Hello again.
As promised, although a few weeks later than originally stated I have finally got round to fully testing my dead PC's power supply.
All functioning - with a nice stable 5.16v on pin 8 of the ATX connector.
So I have stable 12.12v, 5.16v and 3.41v on the relevant ATX pins.
The motherboard LED comes on and stays on, but I get nothing from the PC.
Definitely looks like mobo failure now! Good job the new PC is being delivered in a week.
Thanks for everyone's suggestions, I'm managing to get most of my data back too off the old hard drive. Once I've got as much as I can off and secure I'll try getting Windows to "repair" the disk (it's plugged into another machine)...although I know this can also lead to loss of data. Nothing to lose at that stage though!