Another reason this is a bad idea is that Termini is the wrong direction from Civitavecchia. That train takes about an hour, depending on the local stops. And they might not be the first group off the ship. And they might have to wait to fit on the bus to the train station in Civi.
The penalty for missing the plane on Monday is pretty severe. Do you feel lucky about the 3PM check-in? What month of the year will this be? I would not spend my departure night that far from the airport, even in a country with a less ... er ... Latin reputation for promptness. (In fairness, my Frecciarossa trips have been impressively professional. But I've had delays and failed air conditioning on trains between Venice and Florence.)
The only plus is that the Florence train station is well-situated for some attractions, and has decent hotels nearby.
I realize that I have more disposable income than many other people, but is this your only chance to set foot in Florence in your entire lifetime? There is more than one day to see in Florence, and some of the attractions, like David and the Uffizi can have miserable crowds. Is there lead time to buy discount Frecciarossa tickets, or enough time to get timed Uffizi tickets or (for that matter) Borghese tickets?