2-2-2-4 is fantastic stuff and a regular recommendation from me. Heck the stuff is the price of #10 copper and carries 90A instead of 30A, what's not to like?
I have seen several prominent home off-grid power projects on Youtube fail hideously, because they got "copper-itis" and ran the #10 copper they could afford for a low voltage DC circuit that needed much larger wire. If they had run the aluminum feeder they could have afforded for the price of that #10Cu, their project would have worked!
Do you need a main breaker in the subpanel?
Well, you need a main disconnect of no more than 6 throws.
This is a good argument in favor of getting a nice big panel that isn't HOMeline. Because if you can avoid using tandems, you can turn 3 breakers into 1 throw using a handle-tie intended for 3-phase circuits. (Those ties don't work on tandems). So theoretical 18 circuit limit. Also most larger panels are convertible, so you can just go with a real main breaker if you exceed that.
You can put two 120V circuits on a 2-pole breaker, but then you get the undesirable effect of common trip, so one circuit overloading knocks out the other. So if you want to double-stuff a small panel, you can use dual 240V quadplexes...if you want to go that way, favor Eaton, as they make non-common-trip quads. But that trick only limits you to 12 circuits.
What do you do with ground rods?
Totally separate systems. The neutral comes from the neutral feeder to the neutral bar to the circuit neutrals.
The ground comes from the grounding rods AND the ground wire (different jobs) to the ground bar to the circuit grounds.
They are not bonded together. Two neutral-ground equipotential bonds would cause all sorts of mayhem.
Subpanel on the exterior?
no, interior is just fine. Must have standard working space kept clear at all times, so select an area that people will tend to normally keep clear, like a hallway or threshold.
Does the disconnect need to be outside? No.
What is the easiest way to read NEC online?
cringe
Trying to use NEC as a learning document is a bad, bad idea. And it says so right in Article 90.
Really, an electrical education needs two things: first, a general book on the topic to be a well-rounded primer, i.e. to tell you which questions to ask... and then, a search engine or sources like us to deep drill into particular questions.
99% of the time you will find articles on mikeholt.com, electricallicenserenewal(?).com, ElectricianTalk, or here that will cover your question. Ugol's Law: you're not the only one.
Wire size
I think it's brilliant to choose #2 aluminum.