Win XP 32-bit to Win XP 64-bit

No, 64 doesn't have a media center edition, and you can't "upgrade" from 32bit to 64bit. It has to be a clean install.
 
In addition, there may be another "gotcha" to consider: your drivers. I don't know if there's an easy way to check but make sure there are 64 bit versions of drivers for your devices (especially like printers, cams, network cards, etc)

In any event is always good to create a clone image of the drive before attempting so one can always get back to where they were after a "gotcha" strikes!
 
I wouldn't bother. I would go with win 7 -64bit assuming all your peripherals have drivers.
 
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