La Spezia Centrale station is the most convenient starting point for visiting all five Cinque Terre villages — Riomaggiore (12 minutes), Manarola (16 minutes), Corniglia (21 minutes), Vernazza (25 minutes), and Monterosso (35 minutes). Regional trains run every 30 minutes or so, and the service is frequent enough to allow you to visit two or three villages in a day without rushing.
The Cinque Terre Card covers unlimited train travel between the five villages and La Spezia, plus access to the coastal hiking paths. Buy it at the station or at the Cinque Terre park offices in La Spezia. The famous Sentiero Azzurro (Blue Trail) connecting the villages is partially reopened after landslide damage, but check current conditions before planning your route — some sections close seasonally. Ferries from La Spezia's Molo Italia are a slower but scenic alternative to the train.