Right, so I unstalled Calibre 0.5.14, deleted my library, and then looked in Program Files (x86) for any signs of the calibre directory, there was none, so I renstalled. Same thing happened.
Uninstalled again, and this time did a search of C: drive for all calibre related files and directories. And Bingo! there's the problem. It seems that uninstalling calibre 0.6.x didn't remove the calibre files from Users\<user>\AppData\Local\temp .
Removed those, reinstalled 0.5.14 and it's all working fine.
Thank you for your help Kovid.
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