How to get from Positano to Montepulciano

First, you take the SITA bus from Positano to Sorrento. You could also take the ferry from Positano to Sorrento. Next, you take the Circumvesuviana train from Sorrento to Naples. Next, go upstairs at Naples and take the high-speed to Rome. At Rome Termini, get a ticket from Rome to Montepulciano. You'll change trains at Chiusi. As an alternative to the Circumvesuviana train to Naples and the high-speed to Rome Termini, you can take the Curreri or Marozzi bus from the Sorrento train station to the Rome Tiburtina train station in Rome. The buses run about twice daily and the trip is about 3hrs. Nice buses. Nice ride. The journey from Positano to Naples is about 2.5hrs. The train ride from Naples to Montepulciano is 4.5hrs-5.5hrs depending on the run.

Staci,
Yes, you can go to Sorrento then Naples or you can bus or ferry to Salerno and catch the train. It may be easier to train to Chiusi and then bus to Montepulciano, the train station in Montepulciano is about 10 km from the historic area.

Thank you both for the helpful information!