Whatever you do, do not drive. We're talking hours of winding, narrow roads through the mountains that in some places are only wide enough for one car to pass. There was lots of backing up (in a manual car) on cliffs (some without guardrails) to let cars pass. To top it off, you're sharing the road with Italian drivers — Italian drivers who live there. Capisce? Parking is limited, not close to the center, and the towns are strictly pedestrian-only.
To do a proper tour of all the towns, start on either end — Monterosso or Riomaggiore. You can choose to hike the entire route in one day (it takes around six hours) and then take the train back when you reach the last town. Or stay overnight in a town or two along the way to break up the hike and take it all in.
Or easily see each town by train. Time between towns by train is only five minutes. Just hop on and hop off. As a popular day trip from Florence, you can see all of the five towns for as little as $20! Depart from station Santa Maria Novella to La Spezia Centrale and board the Cinque Terre Express. Piece of cake. The train system in Italy is pretty inexpensive and reliable.