The POR-15 you mention, I just used to line the interior portions of the trunk after removing the old gas tank and prepping the floor surfaces. In my case, I had rust in select areas and used the POR to arrest any further rust. I do plan to paint over the POR.
In my opinion and I don't know if anyone else agrees, but with the POR-15, I would limit to where you have rust issues because, as the product indicates, once you put that stuff on, it'll never come off unless grinding it off. Not even paint thinner will take it off. So I would be careful where you use the POR.
Another note about the POR is to not have it exposed to direct sunlight for it will breakdown from exposure to ultra voilet rays. In your case involving underneath, I need not worry there.
For me having used the POR anywhere on my car, I feel I am biting the bullet using it at all for I am trying maintain quality control, yet trying to keep my restoration as "pure" as possible.
Paul