Yes you can use the printscreen button. The images taken in the game should go to your 'my docs/my games/gc2' folder if you are using xp or 'C:\Users\(your name)\Documents\My Games\GC2TwilightArnor' in Vista. You need to press CTRL + PrtSC to take the screenshot.
I'm pretty sure the built-in screencaps are limited to Twilight, in case you're playing DL or DA. For those, you need a cap tool or you can open Paint and paste after you've pressed PrtScr.
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