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Welcome aboard! And yep, Paizo store's the only place to buy scenarios. The subscription just automatically buys the modules for you. There's no extra cost or savings since the product line is entirely digital; you're fine just buying stuff a la carte. You can get them for free if you're subscribed to multiple rulebook lines or are an official venture agent, but the former's a lot of money, while the latter's a time commitment. That said, if you're thinking of running your games as a Starfinder Society gig, those local orgplay friends you mentioned might be able to hook you up.
There aren't any VTT modules for the post-release scenarios... yet. However, the playtest module includes all four playtest scenarios and two multi-session adventures, and I can confirm that the production value is pretty solid. I've personally been playing on Foundry, which doesn't have a full SF2e system yet, but does have an add-on for Pathfinder 2e that works just as well in the meantime (the two games use the same core rules, so it's easy to mix and match). Even without a module, though, it's pretty easy to rip maps from scenario PDFs and upload them into your VTT of choice. They're a little low-res, but they work (although you can always buy higher res versions separately if you want; I just never do).
Right now, I think the best character manager is Hephaistos 2e (sf2e.hephaistos.online). It's still in development, but it's the most approachable of the small pool of current options. Eventually, there will be a Starbuilder app that works a lot like Pathbuilder (pathbuilder2e.com), but that likely won't come out for another month or two (both Hephaistos and Pathbuilder are solo projects maintained by dedicated fans). Hero Lab is probably fine--some of my Society players use it--but I've never touched it myself.
As for registering and reporting your sessions as part of Starfinder Society, you don't have to do that... unless you think it'd be neat to have your players bring their home-made characters to official convention tables. The whole process is pretty easy to set up (albeit a little archaic). But yeah, all you need is a Paizo account ID number from everybody to get started; the whole point of organized play is to be accessible to everyone. The only extra step I had to take as an in-person organized play GM was ask a few senior members to help me get set up at a local venue. You can read about specific rules and expectations at lorespire.paizo.com, but for a closed table like yours, all you really need to know is how credit and XP awards work.