Santa Maria Novella Railway Station is one of Italy's busiest railway stations, and the gateway into the city for almost 60 million people a year. If you hire a car at the nearby Via Borgo Ognissanti, you'll find yourself close to the north bank of the River Arno, handily placed to explore the city centre a few blocks to the east. It's easy to escape Florence too: the SS67 ring road is just a few blocks to the west.
If you arrive at Florence's Santa Maria Novella train station you'll find Via Borgo Ognissanti a short walk north, close to the River Arno, which runs through the heart of the centre. This being Florence, there's an old church with frescoes by Botticelli in the same street. And within a short drive you'll find most of the major attractions, including treasures like the Piazza della Signoria in front of the Piazza Vecchio, the Basilica di Santa Croce and the Duomo. A short drive across the Arno you'll find the Pitti Palace and the adjoining Boboli Gardens full of Renaissance statues.