What would be the best way to get to Siena from the port of Livorno? Thanks
You should be able to catch a train from there to Siena. The train station in Siena is outside the town, so from the station you can catch a bus into town.
You can take a regional train to Empoli and another regional train from there to Siena. The travel time is a little over two hours. Go here for timetables and fares. Enter a date within the next few days or the fares won't show.
Then, as Scott said, take a bus into town.
Jo,
The solution that Tim provided is spot-on. The travel time using Regional trains is as short as 2H:04M and fare (either first or second class) is listed at €7.80.
The rail station in Siena is at the bottom of the hill. Taking a Bus up the hill is one option, but I find Taxi much easier.
Happy travels!