Ideally you would put "Rust Converter" on first, then primer, then high build primer for paint volume, then the actual paint in three coats. POR-15 replaces the Rust Converter and the primer and the high build primer and the first coat of paint, all applied at once. When looked at it that way it saves time and is cheaper. Then you put two coats of real paint over top of it to seal it, protect it, and provide color. On frames and underside you should use heavy abrasion resistant chassis paint and/or rubberized undercoating to further protect it.
If you use POR-15 by itself it sucks. Its not much better than Rustoleum. I'm not at all suprised the Yukon frame peeled quickly.
I use the Eastwood "Rust Encapsulator" which is the generic brand of POR-15. They come right out and say that its not intended for frame paint. Its a glorified primer that happens to look okay by itself. They recommend removing every little bit of rust you can, then using "Prep" which is a strong degreaser, light etcher, and rust converter rolled into one, then putting the "Rust Encapsulator" on, then putting their "Extreme Chassis Paint" over top of it for protection from abrasion and salt and such. That's exactly what's being done to my cars.