Did not have an opportunity to purchase eurorail pass in advance from Rick Steves website. Where would be best place in Europe to obtain and how? For travel through Italy & Spain.
You can buy certain kinds of passes at the train station in several major cities in Italy, but you'll pay a premium price. For more information, go here. If you plan to take the train from Italy to Spain, you will need to buy a pass that includes France. If you're going to fly from Italy to Spaiin, it may be cheaper to simply buy point-to-point train tickets as you go for both Italy and Spain.
Unless you are doing a lot of long distance train travel, it is difficult to make a pass pay off especially in Italy with the mini fares for advance purchase. Same for Spain.
Thanks for advice & info!
To elaborate on Tim's answer, although most passes need to be purchased prior to arrival in Europe, multi country passes need to be contiguous countries. As has been said throughout this Helpline, passes often wind up being more expensive than point-to-point tickets, especially when considering that expensive "reservation" fees are added for many trains for pass-holders.
There's another way, other than by rail, to go from Italy to Spain, avoiding the need for multi-country train passes. It's overnight ferries from Rome to Barcelona, which leave in the evening from Civitavecchia (one hours by rail from Rome) and arrive the next afternoon in Spain. The ships have everything: from bars and restaurants to music, movies, duty-free shopping, and of course, a choice of comfy chairs, or cabins for two or more people.