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Train takes 1 hr 46 minutes one way; cost is 5,50€ each way. Train station is a short walk, or public bus ride, taxi ride uphill to the walled part of the town. Bus station is apparently more central.
A bus is cheaper, only takes about an hour and 15 mins. and is wonderfully scenic. The bus station in Florence is very close to the train station. Once in Siena, you are dropped in a fairly central spot.
The cheapest way is by bus. It is fun to drive on the highways without having to do the driving yourself. The bus drops you a short walk from the centre of town. Buses are very frequent and convenient.