Questions for experienced game developers regarding learning

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Basically, I'm trying to learn everything I need to know (from knowing almost nothing) to both create 3D models/game assets in Blender and the code/put it together in Unity.

Be aware that both of these (and several of the other necessary skills) are things that people can spend their whole lives mastering. It is certainly possible to learn some of both, but this will necessarily reduce the focus you put into each.

That said, games can be and are made by one-man teams, even today.

The best advice I can give is to start small. Even if a big ARPG is your goal, don't start writing code or making models for that immediately. Start with tutorials that help you build a small functional thing to learn the technologies you want to use, or experiment with those you're unsure of. Then come up with the smallest design you can that covers a portion of what you want to be able to do, and make that - follow a small project through to completion. This isn't wasted time because it wasn't on your ultimate goal project - both code and assets are reusable, and the experience gained is invaluable.

The sample project I sent in with my CV to get this job was a small 2d puzzle game with 10 levels, and fewer mechanics than that. It had no sounds, the player avatar was a shiny ball sprite so I didn't have to animate it when it moved, and it had no menu, settings, or anything displayed other than the levels of the game and I think a game over screen. The fact I'd picked something I could actually complete in the time I had (a few months, while working part time at two jobs), was in my favour, and that still involved enough programming that it provided a decent overview of my skills (including where they were lacking).

Work your way up by developing projects that are a bit bigger than the last, or expand the previous one, rather than jumping in the deep end and trying to make a perfect ARPG right off the bat. The earliest version of PoE (well before my time) was multiplayer asteroids. And even that's not something you should try as your first project (I'd recommend avoiding networking until you've got some more of the general knowledge under your belt).

Good luck.