The best way to get to Cinque Terre is by train or tour bus/van. You most likely will make a connection in La Spezia which is about a 10 minute train ride to Riomaggiore, in Cinque Terre. From there it is roughly a 5 minute train ride between each town.

You need a Cinque Terre card for hiking, free use of restrooms (or pay to use restroom), free Wi-fi at the train stations and unlimited train rides which covers La Spezia, the 5 Cinque Terre villages and Levanto.

You can buy a card at every Cinque Terre train station. I prefer to buy my card in La Spezia as soon as I arrive in order to avoid getting caught riding the train without a validated ticket once I'm traveling through Cinque Terre. Depending on the time of day and year the line can get long but moves efficiently.