Follow Up:
I am using the latest Catalyst drivers from ATI.
I have tested on an earlier system image before the ATI drivers were installed and there is no problem with the bog-standard default VGA driver that comes with XP (though no full featured effects either).
Looks like it doesn't like the latest Catalyst drivers for some reason. Or perhaps the per pixel skinning engine (which is presumably not available with the standard VGA driver) is trying to load Windows XP as if it is a WB skin?
Also: Fiddling with the check boxes to disable per pixel and fix titlebar corruption does not fix the problem, although the titlebar checkbox seems to make the problem delay one change of skin (2 changes and you're out). However, switching that on prevents windows being drawn properly for open windows (right hand side of window missing, titlebar over edge by a centimeter or so).