What will you be using for a mold release? If PVA, I think you could use just about anything. But when you start getting more exotic, you will need to pay very close attention to anything you put on your plug/molds to avoid very bad results, yes, even at the primer stage. Sadly I have seen many chemical reactions over the years, both with my own, and with others that are sharing their builds.
One of the issues I have seen over and over with spray paints is that they continue to cure over a many month period. How do you know when it is done? You really don't, but one sign is if your shop still smells like spray paint when you have been out of the room for an extended time. When I painted cars with rattle cans, I would let them cure in the sun for a couple of months. Then I could come back and polish that spray paint to a point it looked really good. If you didn't give it those months to harden and cure it simply could not take the polish abuse and looked like crud.
There are far better spray paints out on the market, but you will pay dearly for them. You will not find them at any of the discount chains. For my automotive and around the shop uses (and my plane) I like the SEM brand a lot. Good stuff. The cans may be spendy, but they do seem to pack a lot more paint into the can, and it dries faster and cures harder. All good stuff. (Not saying it is right at all for your application.. I have no idea!)
Loving this project, looking forward to each update.