I've finally booked our accommodations and have our itinerary set for Sicily. Here it is:

Fly into Catania (we arrive late in the evening) so 1 night in Catania, Palace Catania
2 nights in Ortiga/Syracusa, Oretea Palace Hotel
2 nights in Taormina, Unahotels Capotaormina
4 nights in Palermo, Grand Hotel Et Des Palmes
1 night in Catania, Palace Catania

The rental car prices convinced my husband we should use the train. We only drive automatic. However, my husband really wants to do some exploring on his own. I figure it would be best to do that from Palermo on our way out. So, renting the car from the airport and do a day road trip on the west coast of Sicily OR rent it as we head back to Catania for our last night in Sicily (although that would mean we don't see much time of Catania).

Questions:

1- Is the airport the best place to rent an automatic car?
2- Where to explore on this day trip? (not interested in the Volcanoes, seen a lot of ancient ruins in our day so eh, love nature/turquoise waters and beautiful scenery including the Norman/Arab history and stopping at small but medieval towns).
3- Do we need to reserve our train tickets in advance or can we just show up at the train station the same day?

Thank you!

First of all, lucky you to be going to Sicily! It's my favorite place in the world.

You not only don't need to purchase train tickets in advance, but you should not! If you have a change in plans you won't be able to use your reserved tickets for a different train. You will be fine buying them at the station just before you leave.
It's good that you are not renting a car because you won't need one in the places you are visiting. In Taormina it's very difficult to drive and almost impossible to park, and in Ortigia tourists cannot park so a car is more of a nuisance, and in Palermo it would be crazy to have a car. Both train and bus travel in Sicily will get you where you are going.

As for your day trip I think it would be better from Palermo, only b/c you have more time there and Catania is worth more than one night. You might want to visit Castellamare del Golfo, a lovely seaside town, and San Vito lo Capo, a beautiful beach area, the salt pans of Trapani and Marsala, and Erice. Erice is a lovely hill town near Trapani. You can drive up and park your car at the Porta Trapani and explore on foot or you can take a cable car from Trapani. If you drive be sure to take the road from Valderice up to the Porta Trapani because it is the easiest to navigate. There's a nature reserve whose name escapes me at the moment that is also worth visiting. I'll try to think of it or maybe someone else will.
As far as the car rental, I like to rent at the airport b/c you avoid city traffic, which can be crazy, especially in Palermo. If you do, it's very easy to get to the places I mentioned from the airport. I did it the last time I was there. I also drive only automatic but I don't know if they are only available at the airport b/c I never tried the city office.
Hope this helps.
Ah, it's the Riserva dello Zingaro right near San Vito lo Capo and Castellamare del Golfo. I knew I'd remember right after I posted. I think you'll enjoy that area based on what you mentioned.

Thank you Panecott! You just planned our day ;-).

I agree that, for your itinerary, it makes more sense to do a day trip out of Palermo. I think you'd also love Cefalù, which is easy to reach by train, but a road trip to San Vito and the Zingaro reserve is also a great option, as is one to Trapani and Erice

Train tickets are for a specific train and seat for Intercity trains, not for Regionale services. In theory, Intercity trains could fill up and can be booked in advance, though in practice they won't in Sicily. For regional trains, you can't book in advance, in the sense that when you buy a ticket no spot is reserved for you, and the ticket is also valid for one-way use on a specific route and for a specific amount of time (I think a day), not a specific train. Anyway, that is all to say you should indeed just buy tickets at the station (or on the Trenitalia app/website) shortly before boarding.

Don’t miss visiting ancient Segesta, not far from Erice.
It is the most haunting site, different from other antiquities sites you will see. Will you also travel to Agrigento? I hope you can.