4.5 Days in Rome

What are some good ideas or walking routes for our late afternoon/evening on Day 1 once it gets dark?

Is this your first trip to Rome? I found the walks in RS Rome to be really good.

https://store.ricksteves.com/products/rome-guidebook?variant=46201267093660

I think San Clemente Church is near the Colosseum and I think that it's a must-see. If your trip is early in November, they may still have the light show in the forum at night.

We went to Naples from Rome on All Saints’ Day a few years ago. We did not realize it was a national day off (Bankers Holiday) and we found the trains and train stations pretty crowded. Do you need to connect in Naples? If I had to do it over again I would have picked a different day to go.

As for sites in Rome there are so many lesser museums that may be quite empty but interesting
We enjoyed the Centrale Montemartini in an old power plant as one example. I know you said you like to eat on the run but there are some very good food tours in Rome. Enjoy

Any recommendations for lesser-known places, unique sites, or quick grab-and-go food spots to fit in on Days 3, 4, or 5?

I would include the Borghese Gallery and the Pantheon somewhere in your itinerary, I wouldn’t miss them. They are not lesser-known places but are not in your itinerary.

What are some good ideas or walking routes for our late afternoon/evening on Day 1 once it gets dark?

Put the iconic places you want to see on Google Maps (Colosseum, Forum, Piazza Venezia, Trevi Fountain, Spanish Steps, Piazza del Popolo, Pantheon, Piazza Navona, Castel Sant’Angelo, St. Peter’s, etc.), and then walk from one to the next. This would give you a good introduction to Rome, seeing a lot of the city along the way. You could spend about 3 or 4 hours doing this, depending on how much time you spend at each place.

Thank you for these replies.
This is not my first trip to Rome but it is for some family members so essentially I am treating it like a first trip. I've not been in 8 years but for a period of 5 years I went twice a year for work (to Florence and occasional trip to Rome). For Pompeii we have an express train from Rome Termini to Pompeii, so no connection in Napels.

What are the best ways to do Appian Way? I know we want to do some of the catacombs.

Just note that fast train from Termini goes to Pompei (town ) not the Scavi

It’s a 10-15 min walk to the site - figure that out ahead of time

What are the best ways to do Appian Way? I know we want to do some of the catacombs

Rick Steve’s’ guidebook has excellent logistics on visiting the Appian Way and a self-guided tour.

I recommend skipping the day trip to Pompeii. Do the Naples area (Sorrento, Amalfi Coast, Naples, Capri and Pompeii when you have 4 days there.

In Rome, recommend the Pantheon, the Piazza Navona, Castel Sant’Angelo (Hadrian's Mausoleum), The Forum, The Capitoline Museums, the Catacombs, The Borghese Gallery and Spanish Steps.
https://www.tripadvisor.com/Attraction_Products-g187791-Rome_Lazio.html

Lots of good ideas here, absolutely add the Pantheon and Borghese Gallery. Lesser known, wonderful sites in central Rome - Palazzo Massimo was our fav & had very few people (the combo ticket includes the Baths of Diocletian & other museums, see my TR below.) Vicus Caprarius, underground museum close to Trevi fountain with Roman ruins where you see the water flowing below you (book ahead on Whatsapp). Teatro Marcello was a delight to walk through en route to Jewish Ghetto. Museum of the Wall on the outskirts of Rome was a really nice break from the crowds (You actually go on the wall & you could take a bike tour there via the Baths of Caracalla.) I think Coliseum tickets include the Roman Forum, so you could do both in one day, I wouldn't but you can if you like that pace.

Consider adding some churches along your route - "St Louise of the French" near Piazza Borghese, what a Baroque gem with 3 stunning Caravaggio paintings. You should see Piazza Novena for the stunning Bernini fountain. And St Ignatius de Loyola, Jesuit Church nearby has an absolutely amazing ceiling. If you want to see the Trevi Fountain, go early, it gets jammed later. Building a saved Google map so you know what's nearby is a good diea. Since you asked about other sites & quick bites, here's our last Trip Report. https://community.ricksteves.com/travel-forum/trip-reports/rome-was-jammed-over-ny-but-still-fun

Pompeii - since it's self-guided, you can go in the Amphitheatre entrance, it's closer to the train station. But I can't even imagine how jammed it would be on a public holiday, check if it's free that day, if it is, Rome would be less crowded, hahaha. Hope you have a great trip!