No real easy way that I know about...
1) Roma Termini station to Napoli Centrale, 22 Euro apiece. Private driver to Positano will be expensive, no doubt more than 100 Euro, but might be worth it. Otherwise, it's Circumvesuviana train from Napoli Centrale to Sorrento station, then bus from there to Positano, which would be a lot cheaper.
2) Roma Termini to Salerno Centrale, then go to adjacent station for bus to Amalfi, at which time you'd change buses to Positano.
Depending on time of year, there is a hydrofoil from Naples to Positano or Salerno to Positano, which would be somewhat quicker and more scenic for sure.