That board and your CPU (most likely) are 64 bit compatible. Anything made in the last few years is.
ASUSTeK Computer Inc.
Going to 64 bit requires a new operating system.
Some versions of Vista offer the choice giving you both options (separate DVDs).
The only 64 bit XP is Server 2003. As named it was intended for servers.
Going over 2 or even 3 GB of board RAM was and still is only seen as an issue for servers. A PC simply does not need that much board RAM.
If you are into gaming the Graphics Card is much more important. The current high end graphics cards run 1 GB of graphics RAM on the card.