A 64 bit cpu runs perfectly fine on a 32bit OS. The only function it loses is the ability to run apps in 64bit format.
As for the Sempron 3100+, in terms of gaming it very well may be better than yours. It depends on the mobo you get though.
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Core 2 Quad Q9550 @ 4.1GHz
Asus Rampage Formula X48
ATI 4870X2 2GB GDDR5 (800/1900)
4GB (2x2GB) DDR2 960
750GB SATAII w/32MB
Creative SB X-Fi Titanium Fatal1ty
SilverStone 750W +12V@60A
3DMark06: 22605
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