I am presuming that you intend to stay in Portofino. If I were you I would take the train from Florence to Santa Margherita Ligure, a three hour trip if you take an Intercity service, then catch bus from the station to Portofino, around fifteen minutes away.
You could alternatively take a 10 minute ferry ride from Santa Margherita ferry terminal or walk (approximately 1 hour - but too difficult with luggage)
If you are staying for a little while try to do a day trip to the CInque Terre villages - 1 hour further along the coast by train)
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