Traveling from Florence to Rome and would like to know what train station to use for leaving from Florence. Thank you.
Probably Santa Maria Novella station out of Florence.
Santa Maria Novella to Roma Termini will probably give you the most choices of departure times.
Why don't you check the website of the Italian railways? Fill out »Firenze« and »Roma« for departure and arrival stations, and you get all the possibilities. If you don't mind being bound to a specific train, you can also buy your ticket in advance (credit card, e-mailed pdf) at a considerable discount.
Actually, you do not get all the possibilities. Between Firenze and Roma you may travel with Trenitalia, that usually offer more choices, or Italo, that has less frequent service at comparable prices but occasionally may be more convenient.
The two most important stations are Firenze Santa Maria Novella and Roma Termini. At this time most train also call at Roma Tiburtina (not convenient for the center, but has cheap service to/from the airport). In Florence trains will call only at one station, usually S.M.N. but some trains direction Verona call at Firenze Campo di Marte to free up scarce time slots at S.M.N.
Santa Maria Novella, or "S. M. Novella" is the main station. My two cents - take an Italo train instead of Trenitalia. We took an Italo train from Florence (SM Novella) to Rome Termini a few weeks ago, and found Italo to be a better, cleaner, friendlier train than previous Trenitalia trips. The website is also easier to use, in my opinion, and the fares (in our case at least) were a few Euros less.
Did you use a Trenitalia's Freccia high speed train? If not you are comparing apples and oranges.
Trenitalia's local trains, called Regionale, are subsidized by regional goverments and are completely different from one (rich) region to a (poor) other.
Trenitalia's high speed service makes profits, therefore they run many more trains that are newer and a little faster than Italotreno's. On the other hand, trenitalia is usually more expensive.