Livorno Day trip to Bolgheri advice needed

[kansaskid]

We are planning to do a DIY day trip to the Bolgheri region south of Livorno while in port from 7am-7pm. We like off the beaten path places (which this area seems to be). A couple questions for anyone who has gone that way:

 

1. Can we rent an automatic car at the port on the spot or are we better off booking the car in advance?

 

2. Any cities/areas to see or not to see down that way? We plan to visit at least one winery and an oil mill which we have booked in advance, but curious if there are others.