borivlikar,
I usually use viamichelin.com to get an idea of drive time. The site is pretty easy to use, and sometimes offers more than one route (e.g. cheapest, fastest, most scenic). It also gives an idea of costs (e.g. tolls). It underestimates the time, IMO, because it doesn't allow for gas/food/comfort stops, so we always add time to theirs....1-3 hours, depending on distance. It will give you an idea of time, however. As you have mentioned, mountain driving will be more difficult than the regular autoroute. Viamichelin.com is a good starting point.
Where to break the journey, I couldn't say. Always observe the speed limits. If caught on a camera you may get a ticket a few months after returning home, plus a fee from the car rental company (to reimburse them for giving your name, etc. to the traffic agency concerned). If you get one, pay it asap as the price goes up fairly rapidly with a delay. Re insurance, we never used to buy the CDW from the rental company, relying on our credit card, but nowadays we buy the insurance for peace of mind and ease of claims should we have an accident (So far so good! Knock on wood!) Insurance costs I don't know. It seems to me when we last rented a car in France, in 2023, we paid less than we expected to. As in the states, take photos of the car in case there are any dings already there.
Note which kind of gas your car takes and learn to recognize the pumps (gasoline or diesel). Have a tap and pay credit card (or debit card) to use for tolls if need be. Get an International Driving Permit (not license!) at AAA (about $20.00, photo needed too) and keep on you, just in case you are stopped for anything. Your state driving license should be current.
Wherever you plan on staying, try to figure out your parking before you arrive there, unless your lodgings have parking on site. Some towns are a pain for parking; others have public lots that are easy to find and access. Better to know ahead of time so you don't spend an hour looking for a place to park when you arrive in a place. In some towns/cities parking is expensive.
Glad you are renting and returning in France. There are big fees to drop in a different country (500-1,000 euros). Be aware of any special stickers/permits needed (like the ZTLs in Italy).
This is probably WAY more info than you wanted, but I hope I have been of somer help. Bonne chance et bon voyage!