I've finally managed to get my Mediator to work. The issue was some of the libraries I was loading with LoadModule - layers.library, graphics.library, utility.library and dos.library all from don_adan on eab. Removing those from my s-s solved the problem I was having with constant hangs when launching the voodoo monitor driver or loading Picasso96prefs.
I also noticed that my ratte monitor switch was not seated correctly as I was just getting a grey screen from picasso96prefs when trying to test voodoo screenmodes. That now works ok.
My machine has been running all weekend with zero issues, the Voodoo3, sb128 and Realtek NIC are always recognised fine, ZorRam 256mb zorro 3 card working with no issue. This is with the latest 3v 4000Di Mk III.
So my attitude has rapidly gone from "this kit is a load of old junk" to "it's completely amazing".