Right well I have done some more playing and it still doesn't work.
I put in the original owners hard drive and had a look around, it doesn't use Picasso96Mode but Picasso TNG which was different there were some different .library files that I copied over. Then I downloaded nicholas's link which gives a more upto date Picasso96....low and behold it also contains TNG!
Uninstalled Picasso96, reinstalled Picasso96, same. Then I went a got my spare CRT (Sony Trinitron Multiscan 200ES). Works perfect on old setup, same results on new setup. I'm even thinking about filming this for all to see......I am so p*^sed off with this now!