XP 32-bit and Vista 64-bit
Core 2 Duo E6600 (dual core 2.4 GHz)
9800GTX
4 gigs DDR2 800
I've placed these in order of what I think is the most important.
1. Use Vista 64, the extra ram does help.
2. MWLL seems cpu limited up to about 3.3-3.4ghz, you would get an amazing boost by upping these mhz (through an upgrade to a quad with high clock speed, or overclocking your C2D if possible).
3. Until you get higher speed, this card won't be your bottleneck.. but when you do, this is the next offender on the list.
4. Upgrading this won't help much, but it would help things load faster.
Now, I know you didn't come here asking for upgrade advice, that's just my take on it all, from reading this subforum and personal experience. Now, on your questions...
quirky-ass motherboard will only allow a 32-bit OS to see exactly 2 gigs of RAMve been getting frequent CTD the whole time
As noted by the developers sometime during the 0.4.x lifecycle, the debugging DLL's returned that OVER HALF of the crashes in the game were caused by insufficient memory.... you do the maths

(I've only been playing for a few days, so I don't have experience with previous versions to compare). My question is this: will switching to Vista to open up those additional 2 gigs help much with either the in-game performance or CTD frequency?
The error reports indicate yes, at the very worst, it can't hurt to try, right?
Or is the rest of my system too old to really have it make much difference? Since I never use Vista (don't think I've booted it on this comp in a couple years), I'll need to do a lot of housekeeping just to be able to run the game on it, not something I really want to bother with unless there's going to be a notable improvement compared to the current setup.
If it gets you a hefty stability increase (via the extra RAM) then I'd say it's worth it... can only take an hour or two tops, short of having very slow internet for patch downloads :p