I've used auto enamel and spray can enamel to finish plugs, followed by multiple coats of 'mold release agent' and one coat of PVA and had no problem. There are better things to use though, if they are available.
http://www.fibreglast.com/
If you want gelcoat and polyester resin to cure so it's not sticky, you block the air from the surface with a RESIN ADDITIVE consisting of paraffin wax dissolved in styrene (
http://www.fibreglast.com/product/Styrene_Wax_71/Resin_Additives ) or you can spray the surface with PVA (
http://www.fibreglast.com/product/PVA_Release_Film_13/Mold_Releases ) or you can cover the surface with plastic, such as when vacuum bagging or infusing.
If you need to do more laminations on the surface, you need to remove the wax, or remove the PVA. With plastic there is no residue to remove, (except of course the plastic) but with all three methods you probably have to rough up the surface with sanding, etc. and you achieve at best a secondary bond. Removing wax is difficult so you get a crappy secondary bond, PVA is water soluble so you get a better bond.
If you leave out or off the air blocks, (wax-PVA-plastic), the surface remains tacky and subsequent laminations, if done soon enough) will have a much better and deeper chemical/primary bond and be stronger than the secondary bond.
It is much easier to work on a convex surface (outside of a bowl) as compared to a concave surface (inside of a bowl).
When you make a plug, you want to get the finest surface you can get, ideally you get it as smooth and shiny and polished as the finished product is going to be. If the plug will have convex and concave areas, the convex areas should be finished to perfection. The concave areas should be finished as much as possible. When the mold is made, those concave areas will become convex and can be finished to perfection on the mold itself.
So, when making the mold from the plug, the first step (after waxing and PVAing the plug) is to coat the plug with UNWAXED TOOLING gelcoat (
http://www.fibreglast.com/product/Orange_Tooling_Gel_Coat_just_gel_coats_188/Polyester_Resins ). After that is set, the rest of the laminations will be applied using UNWAXED LAMINATING resin (
http://www.fibreglast.com/product/Polyester_Molding_Resin_just_resin_77/Polyester_Resins ) so each layer will have a primary bond to the previous one. The last layer of the mold can use waxed resin, PVA, plastic to end up non-sticky, or unwaxed resin can be used and the outside of the mold painted. Latex paint works fine.
When you take the mold off the plug, it is pretty much ready to go, maybe needing some light buffing and polishing.
To get a part from the mold is pretty much the same process.