OK I have found another angle on this and I am groping towards an idea of what the difference is.
Right clicking on a folder in C:/users[username]....gives option to move a physical system folder location and this is what I have been trying and getting very odd results - even when selecting to move all files. This is all I have seen suggested anywhere I have looked on the web.

By
kevvyb at 2009-07-25
What I have done is gone in from the 'virtual folder' end (not sure if that is the correct term). Right clicking on the virtual folder Pictures for instance give the option to add and remove save locations to this virtual folder.

By
kevvyb at 2009-07-25
Can anyone clarify the difference between these two approaches? I think the difference is that the first leaves a default save location for the 'physical' folder on C: at users/[username] or moves that to another location (supposedly). This is what I had trouble with.
The second I think makes no changes to the location of that system file and instead gathers save location(s) for the virtual folders. I have added folders on my D: partition (currently the Win XP 'My Pictures' folder) and removed the C:/users/public and C:/users/[username] locations.
And this I think has achieved what I desired. The pictures virtual folder remains and and files saved there will actually be saved at D:/My Pictures.