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I currently have an S95 and when I am taking pictures I try to do it in full manual and then let the exposure meter tell me where the correct exposure should be. I assume the built in meter is pretty accurate and what I should go by, but are there instances when I should ignore it? Or will those times, if ever, only come once I have a lot more experience?
Also, as far as white balance goes, I have been leaving that on auto (actually just forgot to even think about that setting). Would AWB be ok to shoot as a beginner and then try to pick up that part of shooting later, or should I try to adjust that manually as well?
The built-in meters are pretty accurate on the exposure, as long as every element in the frame roughly averages about the same in gray scale density. Meters are designed assuming most picture elements are equal to a standardized density of 18% gray. If your main subject in the frame varies from that standard, or the majority of everything else (foreground/background) is brighter or darker, then your subject will be over/underexposed accordingly. That is where digital really shines, in that you can take test shots, view them on screen, and adjust your exposure manually until the main subject is correctly exposed, as long as the lighting is consistent. I use the spot metering function on my camera a lot for that reason if the light will be varying quite a bit, and shoot in Av priority. Sometimes I use exposure compensation as well. But if the light will be the same most of the time, manual is the way to go.
Most cameras will handle most shooting situations quite well in AWB mode, I have found. The main exception is indoors, where many do not handle incandescent and fluorescent lights, especially a mixture of the two, very well at all. That is when shooting in RAW really helps, it makes fixing WB in post-processing much easier.