I'm in MA, so I'm not the expert but I do know the state a little bit. Sorry in advance for the scattershooting.
First thing to know, Maine is huge. Not Texas huge, but way bigger than anyone realizes. I had a friend in the Reserves who would do his drill weekend south of Boston who always talked about his 8 hour drive to get home to Mars Hill (up in the top part, but not at the very top).
There's good highway access across the eastern side of the state, but if you start venturing west at all, it quickly turns to winding 2 lane highways. Portland has a pretty good airport.
If I were looking to move there, I'd look at the western part of the state, personally. There are a few big ski areas, if that's your thing (Sunday River, Saddleback, Sugarloaf). I want to restate that it is REMOTE out there, with your nearest "city" being North Conway, NH, or potentially Augusta.
If you're into politics, Portland is liberal. Lots of Boston WFH transplants moving there. The rest of the state, not so much. I used to date a girl from Bangor who called it "the South of the North." Bar Harbor area is awesome, but is a super tourist destination, so If you want to settle in that area, don't expect family and friends to casually be able to visit and find a place to stay nearby during peak seasons (I was making plans to go with a girlfriend for 4th of July one year, but rooms at the Comfort Inn about 45 minutes away were $600/night and it only went up from there).
Unlimited options for hunting and fishing across the state, and Baxter state park is designated as a dark sky zone, so great star watching there, if you're into astronomy.
There is an income tax, so if you're looking to the western part of the state, consider jumping the border to NH (no income or sales tax).
French Canadians abound up there. I haven't had many interactions with them, but those that I have had, they've been pretty rude and they do not tip, so they piss off waitstaff if you're out eating and a bunch of them are there, expect it to show on your servers' faces.