Itinerary help Cinque Terre and Tuscany

Train time to Florence from the CT areais 3 hours. Rent your car in La Spezia [probably Hertz]. We arrange our cars by calling up the broker Autoeurope; get zero- deductible collsion, which covers any damage to the body of the vehicle. Read this about driving in Italy and restrictions involved [ZTLs]; avoid leaving anything of value in a car when parked:

http://driventoit.blogspot.com/

Flights on www.skyscanner.com. Why not a Pisa round trip? Dump the car at the airport, taxi to the Hotel Bologna for an overnight; free airport shuttle.

Because of ZTL isues, returning a car In Florence it is suggested to navigate to Via Palagio degli Spini, the complex near the airport. Doing that on the flight day you mention would be very risky, as a return there can take quite a while.

Exactly how many days with the car will you have? Driving route planning on www.viamichelin.com, the + sign for multiple stops. Greve is not a favorable location for the places you mention. If planning an Orvieto visit there are things you need to know.

Here is the La Spezia port schedule:

http://crew-center.com/la-spezia-italy-cruise-ship-schedule-2020

Why CT first? Why not last? Final night in the departure city the night before the flight? With 2 weeks, maybe 2 stops on the road. There is a terrific hotel right below the walls of San Gimignano [10 minute walk up to town], the Relais Santa Chiara, reasonable drive from the Pisa Airport. Note that SG gets hordes of tour bus visitors. Then move south [hotels on booking.com].

https://www.wanderingitaly.com/maps/valdorcia.html

We stayed in Levanto when we went in April a few years ago. It was very convenient, and we loved the more "local" atmosphere. The train connections to the five towns are very easy - you need a pass because it is a National park of course. The issue with Holy Week/Easter we found was with travel - EVERYONE was traveling home by train with packages. Also we had off and on spring rain - not good for hiking but plenty of sun for cafe lunches and apertivo.

The train to Florence is easy enough, but you may want to take the shuttle bus from the station out to the airport and rent the car there when you are ready - makes returning it easier on departure. "Central" in Tuscany may be considered geographically as a location, or as a place with really good road connections to where you want to go. The local roads are lovely but can be windy and slow, compared to being near major routes to locations that you want to visit. On one trip to Tuscany we stayed at a well-recommended Agritourismo which was lots of fun, and very central, but a long drive on local roads to everywhere. You might want too watch the RSA Tuscany Videos and the most updated version of the guidebook to identify opportunities. You have already identified more than 2 weeks of things to do/places to go so have fun paring them back.

On our trips we have really enjoyed staying in Florence at the Loggiato dei Serviti hotel 4 blocks north of the Duomo, and usually return there for the night before we depart. If you are considering at least a day trip to Florence as part of the itinerary you might just head there a day early and not have to go back and forth.

https://www.loggiatodeiservitihotel.it

Fly into Genoa, train to one of these Italian Rivera towns. Camoglia, Santa Margherita Liguria, Rapallo and Portofino ( just visit this one). All under an hour. About the same distance from the Cinque Terre Villages.
You could visit both areas from this local.

To reach Tuscany, pick up your car in either Levanto or La Spezia. Drive time between 2-2 1/2 hours to Greve.

Spend your last night in Florence after dropping the car. Tram or taxi to the airport. 20 minutes.

The Italian Rivera towns noted above are where I have stayed; limited flights into GOA.

“The train connections to the five towns are very easy - you need a pass because it is a National park of course”

You do not need a CT Card to take train trips. Daily cards are €16/pp, include 4 train rides on the regional lines between the 5 villages [plus other benefits]. For train rides only a lousy deal. Also keep in mind that when the villages are crowded, train travel is not advised between the hours of 10 and 5. Plus there are Intercity trains between Pisa Centrale and Monterosso.

For tickets not purchased online, get the Trenitalia app to avoid wasting time at machines or windows. There are also security issues.