Duratec is the industry standard (at least the marine industry;)) for coating plugs. You don’t need the Duratec thinner, regular lacquer thinner works perfectly. Invest in a mixer (the kind you chuck into a drill) as the fillers settle. Mix thoroughly. Mix in the thinner. And don’t forget the catalyst. Depending on the temperature and size of the project, I’ll mix anywhere from one to two percent MEKP. Only catalyze one cup at a time and watch your time (ten to fifteen minute gel time). Strain the thinned and catalyzed primer into the cup. Promptly wash gun with lac thinner or acetone.
The gun you linked to should work fine The 1.8 mm tip is good for primer. You want to spray fairly wet or you’ll end up with a pebbled surface which requires a lot of sanding to smooth.
As for PVA on the mold, it works but the mold surface is nowhere near the quality of a mold built over a properly sanded and polished plug. If you prepare the plug with release agents, you should have no trouble with sticking. I’ve built hundreds of molds and never PVAed one of them. 6 to 8 coats of a mold release wax and the plug and mold should separate with a couple of wedges. Polymer release agents like Freecoat are also available.