Yes, OK. Here's my default startup .tgd attached. Happens everytime, I just never got around to mentioning it before.
You'll notice there is an existing painted shader in the group 'etc's'.
If I try and click on the paintbrush button, the only option I have is 'create new'. Once it's created, though, the first one is back in the list when you click the paintbrush button again...
EDITED: I've made sure that all nodes were captured inside their groups, I noticed in the .tgd in notepad that my default paint shader wasn't in its group. Fixed that now but it still happens. The new file is attached, everything seems set up correctly, it still doesn't find this shader though first time.