Woohoo! Thanks for the review. We are basically doing your trip, but in reverse. Rome->Positano->Florence->Venice.
Other than hotels, we haven't planned much. I'm planning on purchasing our rail tickets this week, (I'm very go with the flow on vacation, but I like to have transportation figured out), and thanks to the advice of the ladies on here, I think we're just going with a private car to take us from Naples to Positano. I think I'm most excited about that part of our trip. Our hotel looks amazing (it was our splurge), and we're planning on hiking the Pathway of the Gods, and just exploring. We might do a private boat tour around Capri.
In Venice, I booked a hotel in the Dorsoduro neighborhood. I researched this a bit, and it said to select this area if you wanted to be close to sites, but wanted a more authentic, neighborhood feel for bars and restaurants. We'll see. We're also planning on jumping over to Burano for a bit.
We're planning on renting a car for one of our days in Florence. Was it difficult to get out of the city? What car rental place did you use? Which wineries did you visit, and did you have to schedule it ahead of time? LOL Sorry for all of the questions. Right now, I was planning on booking a wine tasting and lunch here: fattoriapoggioalloro.com/?lang=en and then maybe walking around San Gimignano, but I'm still looking around.
I'm so excited, and I still have to wait 4 months for our trip.