My old AMD dual core system has 4GB of RAM and I have Vista x86 installed on that, and an 8800GTX graphics card, and it can address 3.5GB of the 4GB..
I would definitely use 4GB even though your only using XP, I remember when I was using 2GB of RAM and running XP, it was fine for games and stuff, but when I upgraded the RAM to 4GB I saw a nice boost in general system performance.
Like when I wanted to Alt-Tab to the desktop out of a game, when I had 2GB of RAM this just wasn't possible, it took forever to get back to the desktop, and when you tried to go back into the game, it took just as much time for the game to start back up.
But once I fitted 4GB this was no longer an issue, and everything else just felt snappier to..
Definitely worth going for 4GB over 2GB imo..