Andy,
I have just tried to delete the cache again and re-sync one of my share point sites. After I clicked on "sync" in my browser (IE) and Skydrive opened, I got the following error:
Problem signature:
Problem Event Name: APPCRASH
Application Name: GROOVE.EXE
Application Version: 15.0.4551.1508
Application Timestamp: 527972e7
Fault Module Name: GROOVE.EXE
Fault Module Version: 15.0.4551.1508
Fault Module Timestamp: 527972e7
Exception Code: c0000005
Exception Offset: 00075103
OS Version: 6.3.9600.2.0.0.256.48
Locale ID: 1033
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After that I had the option to either (a) Search for a solution and close the program or (b) Close the program. Searching for a solution online did not help. Now, when I start my Skydrive, nothing really happens and it just says "get started".
Is this error code of any help for you?