Yes, a quad-core is quite similar to a motherboard with four single
CPUs on it. Right down to the bottlenecks of all those cores having to
fight for the same memory bandwidth...
If your main target is games, then I suggest getting a dual-core 3.0 GHz CPU instead of a quad-core 2.3 GHz CPU. Current games typically use only one or two cores, so the four cores wouldn't be able to help out enough to compensate for the lower clock frequency. Some games will scale up on four-core CPUs, and some other tasks (like building large projects, or ray-tracing) will also scale pretty well to four-core CPUs, and if those are your main concern, then a quad-core is the better choice.
256 MB VRAM is not enough for modern games -- especially if you're thinking things like Crysis. If you want to play games, you want a real graphics card, which means 512 MB RAM or more, and a graphics card where the third digit from the right is 8 or 9 (so it's a 256-bit card with good fill rate). Thus, ATI 3800, or GeForce 8800 or 9800, are what you should be looking at. Personally, I go with NVIDIA, because I find their drivers to be more stable, but it's a personal preference kind of choice.
Yes, 32-bit programs run on 64-bit OSes, by and large.
I would go with Windows Vista, especially now that SP1 is out. In fact, I'm running 64-bit Windows Vista on my dual-core, 3.0 GHz machine with a 512 MB graphics card (I was in the same situation as you a while back :-) and it's great!
No, I don't think the educational version allows you to upgrade to small business Office. There is, however, a "home user" version of office, which is fairly affordable -- on the order of $150. You can typically find it at places like Costco. Also, if you're going to do a lot of development, it might be worth getting a MSDN subscription. The cost is higher (four digits) but you get free access to almost everything MS does, for development and testing purposes. This includes office, operating systems, servers, etc.
Jon Watte, Direct3D MVP
kW X-port 3ds Max .X exporter
kW Animation source code