It depends what you think is important (and not a guide book, or randos on the internet).
Every transfer is holiday time wasted: Packing bags; lugging them down to reception; checking out; getting to the transport (in this case the car hire firm, filling out their forms etc); the journey from A to B; navigating to the next base (including issues with ZTLs if central); checking in; unpacking bags; getting your bearings in the new place.
That’s not to say I don’t do transfers, but on a 5 day holiday, they’re not a great option unless it’s planned as a ‘road trip’ from arrival to the airport, to departure from the airport. Day trips may end up with similar or longer distances covered, but without the luggage and hassle, the day trip journey itself can be a pleasure (e.g. we love the fast modern Freccia trains).
Given it’s November, the weather can still be decent, but you have less daylight hours, so we tend to lean towards a town or city stay, rather than being in the middle of the countryside. i.e. it’s not as good for exploring the region as (say) May or October. That said, a sunny early November walk through vineyards remains a joy.
Barry’s comment about Firenze is worth noting. Staying outside with a car leaves you the flexibility of easy (maybe using the bus or a pre-researched easy to access car park) day trip into the city. The beauty of the buses are they typically drop passengers right in the centre, whereas the train stations in Toscana tend to be outside the centre. It also gives you a peaceful retreat away from the city and other tourists, plus if planned well, has you avoiding having to head towards the city on day trips out and about.
I like Bologna as a day trip suggestion in November, as whilst it’s busy, it’s big city busy more than tourist busy, so will give a nice contrast. The trains (trenitalia.com) are fast and reliable, with trading up to 1st often v. cheap when booking in advance. Bologna has extensive porticoed streets, so even if it’s raining, you’ll often be protected. The food shopping is exceptionally good, and that allows for a picnic to be procured for the return journey. Note however that the train station is a 30 minute walk from the centre (or cramped bus ride or taxi).
Lucca certainly in reach of Firenze and it makes for a lovely compact day trip, plus its train station is reasonably close (just outside the city walls, so 5 mins to get inside). Both Lucca (Enoteca Vanni) and Firenze (Enoteca Pitti Gola) allow a wine geek to indulge, without venturing near a winery, plus there will be other enoteche (for drinking or buying).
Pisa also an option, but avoid the obvious tourist routes to the field of miracles and do make good time for the city itself (see more on this above)