Thanks so much for all the suggestions, guys.
I am very much inclined to agree that iffy PSU voltages or capacity can lead to instability. But you've gotta think those things would arise when you're stressing the PSU. I get freezes when everything is idling.
I believe I have managed to pinpoint the problem to the mobo. Today I went through the giant pain in the ass of switching in an older but working WD hard drive and testing with it. Got the same issue with it, and this drive is PATA, which means different power and mobo connectors, thus eliminating any faulty cable issues. All important fans spin up and everything seems to work fine, got a big fat zalman heatsink on the CPU so it's kept at a pretty cool temp. I even touched the heatsink to test if there's good heat dispersion after using the computer for a while, and yep heatsink was warm all over. So it's not a case of a bad connection between the chip and heatsink whereby the chip might overheat.
Nope, finally today messing with the HDs, I noticed that there's a fan on the mobo which doesn't actually spin up when it's turned on. I think it's on the north or south bridge, has a teeny heatsink on it, but presumably really needs the fan in order for it not to overheat. I've no idea when this thing stopped spinning, it did when i first put the thing together. But my question is, does an overheating north/south bridge typically lead to this sort of freeze-up?
It's pretty much unfixable since the fan plugs into the mobo itself. I was already thinking of buying a new mobo, so this just confirms my suspicions. Now I have yet another favour to ask - could someone with more seniority than I check the trading forum to see if there are any shuttle SN95G5s available? It's the only thing that matches up the rest of my hardware and it's pretty much impossible to find nowadays.
Sorry for being so prosaic