I’ve never played a Paizo game but I am familiar with Roll20. Can’t say I’m a power user or anything, but I’ve played in AD&D 2E and 5E games since 2016, now DMing my own weekly 5E game for the last year. They offer support for a bunch of other games as well.
Depending on the ruleset you use, some of the official documents are cooked into the platform, like character sheets if you’re using 5E SRD. They shouldn’t be too complicated - they even have chargen wizards (the script kind, not spellcasting kind) that take new players through all the basic steps. I think Pathfinder is inherently more complicated than modern D&D, so that may be a reflection of then system rather than Roll20 itself.
I also haven’t used any of the assets from the Roll20 store, so I can’t make a recommendation one way of the other.
There are other platforms, too, probably the most popular being Fantasy Grounds. However, I believe it requires everyone to buy a copy to get all the features, is not cheap, and so is not necessarily suited to first-time players. It still might be preferable over Roll20 for a group of friends who are already familiar with the game.
In my experience, the hardest part about playing on Roll20 is finding a game in the first place, or one that feels like a good fit.