If you are traveling on a weekend I would recommend making reservations and buying a ticket online or buying from the machines earlier in the week. The cost is the same either way. The official website is www.trenitalia.com and there is a page in English if you click in the top right corner. One of the most important things to know is the name of the stations (i.e. Roma termini to Firenze S.M.N. (Rome to Florence)) as there could be more than one station for bigger cities.
The ticket machines are easy to use and there are a few kinds. I used the gray ones which accept credit cards and offer very easy instructions in several languages. They give you every option for travel on every type of train they have running. Believe me it seemed as if they had a train running every 1/2 hour all day so I don't imagine you'd have a problem or that they'd run out of reserved seating (unless it were a holiday).
If you want a cheaper fare there are slow trains (about 3hrs between Florence and Rome). For smaller stations these are sometimes your only option (I rode one between Florence and Pisa in 1 1/2 hrs). You do not need a reservation for these but if you opt for this fare get there early enough to grab a seat, otherwise you could end up standing. Just remember to stamp it in the yellow machine before you board. You will see them as you are walking to the train.

