first of all i would design the parts in a way that there is a channel inside so you can thread them onto two aluminum square extrusions or similar so the individually printed parts are well aligned. then superglue everything together. doublecheck everything is straight and the tolerances are as needed.
then i give the parts a rough sanding with a block and 120 grit sandpaper, then some bodyfiller to smooth out some iregularities, followed by sanding again. sanding is really nice as the ridges from the printed layers will give you indication of how deep you sanded. And keep things cool while sanding as the PLA doesn't like heat at all. So i do all sanding wet.
Then from here on i will give you two ways of doing it. the right way and my way. I recommend doing it the right way and if you wanna do it like me, then absolutely test material compatibility in a small scale test!
The right way: Use a 2K body filler sprayed on the whole part and block sand. repeat until you have the desired finish. Then spray a 2K paint on the whole part and let it cure perfectly. this can take a while but you will have heaps of problems if the paint is not cured. then you can proceed with a chemical mold release or wax and build your mould on this. Another alternative is to use a coating resin to coat the plug with, but this is a whole lot more work to sand to a perfect finish, and it is more likely that you will burn through the layer and will have spots where the mould doesn't release.
As I am not super well equipped for painting 2K paint and i know i can get away with the following: Paint the whole plug with
duplicolor spray putty to fill in bigger sanding scratches, then finish off with a layer of
duplicolor spray filler, which i sand up to 800 grit usually. Once finished i let the paint dry overnight in an oven at 35...40°C. This is super important. As This spray paint is not resistant to solvents I then use Formula five paste wax (which is a really nice product anyway). I give it at least 3 coats. The wax will leave you with a nicer finish than the 800 grit sandpaper would make you believe, as it fills in micro scratches. Your plug is then ready to make an EPOXY mould. do not try to put on anything styrene based onto this surface...
I hope this gives you an idea.
cheers!