Ok, I'm not sure who all has VR, but I have a Vive. I'll be putting comments regarding content here.
First off... Huge huge huge deal to get whether you have a Vive or Oculus... Get Vorpx or something similar. I was able to get it working in both Arma 3 (single player) and Fallout 4. Freaking cool. Wish the resolution was higher, obviously but still very fun to tool around Wasteland Boston in VR. Arma... geez, the depth perception on it was amazing. It felt real. Now, be aware, trying to run Arma on VR has to be pretty taxing. I'm using an 8 core processor and a 980 GTX. Ran fine for me but not sure how well it would on other systems since it's having to keep up with the CPU hog of Arma and head tracking.
As to actual VR titles...
theBlue
First thing I bought was theBlu. It's an underwater simulator and not a game as much as an experience. There are three "experiences"... a Blue Whale encounter, coral reef, and deep sea trench. Absolutely stunning. Got the wife hooked up into it and she was just saying wow over and over again. I can actually just get into that program just to relax, it's very chill. One cool thing with the Vive is that the deep sea trench uses one of your controllers as a flash light so you can look around and see what's there. The limited field of view actually enhances the reality here because it feels like you're looking through a dive mask. Anyone who gets a vive, I HIGHLY recommend this. Blue whale encounter can be downloaded for free but the other two are both 10x better than the whale.
Job Simulator
This is a freebie that comes with the Vive. It is FUN. The basic premise is that it's the future and humans have died but computers are still around. This is a museum about human life and since we spend as much time at work as we do doing anything else, it makes sense that there would be a museum about us working. There are four jobs... checker, auto mechanic, cook, and office worker. Lots of references to different things and it is a fun way to get into VR gaming. JS is very simple and the graphics are pedestrian but it feels like you're in a cartoon. Actually, the way the colors and the animations are, it really feels like you're in a future where the human race died out on the Simpsons. It's funny and a great intro into using VR. I blasted through half of the game in two nights.
Fantastic Contraption
Another freebie and it's cool though didn't hook me as much as JS. Basically, you build machines to move stuff around. Fun to work with but nothing overly exciting for me. I found myself throwing things around in the VR space more than building.
VR Desktop
Not a game but a great app. Turns your desktop into a VR friendly environment. Lots of controls and the ability to play 360 degree videos directly in app. It's $15 but worth it.
Space Pirate Trainer
Insanely fun. It's very simple... Space Invaders in VR. Drone keep coming at you in waves and you have to shoot them down while dodging their shots. You have different styles of guns (single shot with a laser, full auto that you have to lead the target with, a laser shot and a laser beam.) You also can use a shield. I tend to run with a shield in my left hand and a single shot in my right, but will move to full auto at times. So far this is my favorite game and it is acually pretty aerobic. You're shooting, turning, dodging, blocking... I worked up a pretty good sweat every time I've played.
First off... Huge huge huge deal to get whether you have a Vive or Oculus... Get Vorpx or something similar. I was able to get it working in both Arma 3 (single player) and Fallout 4. Freaking cool. Wish the resolution was higher, obviously but still very fun to tool around Wasteland Boston in VR. Arma... geez, the depth perception on it was amazing. It felt real. Now, be aware, trying to run Arma on VR has to be pretty taxing. I'm using an 8 core processor and a 980 GTX. Ran fine for me but not sure how well it would on other systems since it's having to keep up with the CPU hog of Arma and head tracking.
As to actual VR titles...
theBlue
First thing I bought was theBlu. It's an underwater simulator and not a game as much as an experience. There are three "experiences"... a Blue Whale encounter, coral reef, and deep sea trench. Absolutely stunning. Got the wife hooked up into it and she was just saying wow over and over again. I can actually just get into that program just to relax, it's very chill. One cool thing with the Vive is that the deep sea trench uses one of your controllers as a flash light so you can look around and see what's there. The limited field of view actually enhances the reality here because it feels like you're looking through a dive mask. Anyone who gets a vive, I HIGHLY recommend this. Blue whale encounter can be downloaded for free but the other two are both 10x better than the whale.
Job Simulator
This is a freebie that comes with the Vive. It is FUN. The basic premise is that it's the future and humans have died but computers are still around. This is a museum about human life and since we spend as much time at work as we do doing anything else, it makes sense that there would be a museum about us working. There are four jobs... checker, auto mechanic, cook, and office worker. Lots of references to different things and it is a fun way to get into VR gaming. JS is very simple and the graphics are pedestrian but it feels like you're in a cartoon. Actually, the way the colors and the animations are, it really feels like you're in a future where the human race died out on the Simpsons. It's funny and a great intro into using VR. I blasted through half of the game in two nights.
Fantastic Contraption
Another freebie and it's cool though didn't hook me as much as JS. Basically, you build machines to move stuff around. Fun to work with but nothing overly exciting for me. I found myself throwing things around in the VR space more than building.
VR Desktop
Not a game but a great app. Turns your desktop into a VR friendly environment. Lots of controls and the ability to play 360 degree videos directly in app. It's $15 but worth it.
Space Pirate Trainer
Insanely fun. It's very simple... Space Invaders in VR. Drone keep coming at you in waves and you have to shoot them down while dodging their shots. You have different styles of guns (single shot with a laser, full auto that you have to lead the target with, a laser shot and a laser beam.) You also can use a shield. I tend to run with a shield in my left hand and a single shot in my right, but will move to full auto at times. So far this is my favorite game and it is acually pretty aerobic. You're shooting, turning, dodging, blocking... I worked up a pretty good sweat every time I've played.