OK, folks, riddle me this if you can:
I fixed this problem as a by-product of fixing another one, apparently unrelated, which was that I couldn't access the workstation's DVD drive - I just kept getting the dreaded "Access is denied" mantra. In my searching, I came across a suggestion to uninstall the drive and reinstall it. Seems kinda extreme, but it would certainly initialise its security settings.
Well I did it, and sure enough I now have full access to the drive, but then when I opened the Backup toolbox to create a new system repair disk, I found the backup to my system servers is now working, along with correctly identifying the DVD drive and an external USB HDD I have connected as usable backup devices (which it didn't before).
It makes about as much sense to me as getting your TV to work by turning the kitchen tap on, but there you go - that's Windows for you.