1) Depends on what you play, but probably. I have played Skyrim on 2GB of RAM before (with a decent framerate), but that is not recommended. Your computer would probably benefit from more ram, but here is how you can tell:
>Next time your are playing a game, get into it a bit, then press Alt + tab
>Press ctrl + shift + esc
>Click on the Performance tab
>Look for a little box that says memory just above it. It should have a bar that is partially illuminated and under that bar should be a number of GB. That is the amount of memory that is currently being used by your system. If it is anywhere above about 3GB, then more RAM will probably benefit you.
2) Yes, you can do that. Some motherboards give priority/better performance to certain slots, so if that is the case with your motherboard, you should put the 4GB sticks in those slots. This information should be in your motherboard's users' manual.
Edit: I am assuming your motherboard has at least 4 physical slots for RAM. If not then you will need to replace your current RAM rather than adding to it.
Good luck, and feel free to contact me, either on this thread or by PM if you have any further questions.