The biggest issue is the neutralise any rust with a rust converter before putting underseal on it. There is plenty on YouTube about the application of rust converters.
The problem is unless your using paint shop grade material then very few of them actually work,. When I bought my truck I machine cleaned the underside, de-greased it, rust treated it, applied a coat of industrial red oxide primer and finished with a coat of Dinitrol 1520p, which is the stuff they use to protect electricity pylons. It lasted about 6-12 months and then started to break up. The next time we wire brushed the metal work, removed the sump, 'box guards and spare wheel and sprayed a few litres of Tetra Schutz Underbody Seal. This has lasted very well and even thought the underside wasn't spotless, or certainly as clean as I would have liked, the Schutz stuff is very sticky and flexible enough to stay intact. The 'hard' paint system I used initially simply won't stand up to constant bombardment from the stonechips, salt, mud etc whereas it simply bounces of the Schutz. Periodically I put it up on the ramp and and just maintain any sections that are in need but on the whole I'm very impressed. It's no substitute for Waxoyl and the like but it works well when used in harmony with it.