I’ve never done it, but I can forsee a few problems that MIGHT arise.
A S&W revolver is pretty finely fitted. I’d think you would need to mask off areas where dimensions are really tight.
Examples of these would be the edge surfaces where the sideplate fits into the frame (not normally visible), the ratchet and mating areas in the cylinder and frame, and maybe even the locking notches in the cylinder.
I also suspect the bolt will wear a groove in the cylinder pretty quickly. This kind of wear happens on blued revolvers anyway, but I’m wondering if a painted-on finish might chip instead of wearing evenly.
Personally, I’d be tempted to not refinish the cylinder at all (though the appearance might be too garish for your taste).
Just my thoughts FWIW. If you decide to do this, please post photos of the revolver after it has been used a bit.