About to dual boot Windows 7 Ultimate 64bit and XP Ultra 32bit

Alright I have been using Windows 7 for a few months almost since it came out and I love it. I finally bought my retail version and am about to install it on my 500GB HDD. The only problem is that I use Windows 7 for gaming and high ram usage programs so I use the 64bit version. I also do a lot of flash and photoshop work though and those programs do not seem stable in 64bit so I want to dual boot with XP which I have a 32bit version of.
I have done this before but not with Windows 7 is there anything particular about Win7 that I need to know about first that would make this more difficult that normal?

PS: I added a 1TB HDD recently and I was being stupid because I was like, "Drive (Z)! That sounds great!" Well obviously now it is at the bottom of my drive list but I access it more than any other drive. I know that I can rename it and I know how but when I go to do it, I get a warning message (which I should have known would pop up) "Many programs use the Drive letter to access files. Are you sure you want to change?" Will I need to go through and change the paths of all of the programs that need files there, like I'm running Steam (a video game client) from the (currently) Z drive, well it no longer work if I change the drive to "A"?

Thanks a lot for your help guys!

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