You just missed the preview 64-bit version of XP. They aren't allowing downloads or sending CD's anymore but you might bump into someone who already downloaded it.
As for your current 32-bit XP, yes, it'll run in 32-bit mode, but faster. The performance differences most people notice (besides possible clock rate) come from instruction efficiency, larger cache, and an improved memory interface. For no other reason go with a socket 939. The 754's have a single-channel memory controller vs. the 939's dual. Anyway, desktop socket 754 is nearing end-of-life.
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