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I bought a couple cheap secondhand Rhinos to Nurgle-up for my death guard. It's an awfully big model to strip the paint from though. Does anyone know what would happen if I just started applying green stuff and other modifications right on top of the paint, then repainted the whole thing?

Should work pretty much like bare plastic for green stuff. I've never had trouble putting green stuff on acrylic paint. If the paint is super smooth you can do the same as you would on a metal model: put a few scratches in the area you are guaranteed to cover with green stuff for proper grip and work normally from there.

Gluing on extra bits depends on which glue and material you're working with, along with how thick the paint is. Acrylic paint one or two layers deep won't get in the way of plastic cement welding two plastic pieces. Oil paints will. Super glue doesn't care what the surface looks like as long as it's reasonably flat.

Yeah but with superglue the strength of the join is then the weaker of the 2 bonds. Superglue to paint or paint to original surface.

In the worst case though, if the superglue or GS come away because the paint loses its bond, you can always just superglue it back on again for a better bond.