I don't have any concrete answers, but I'd love to participate in this conversation. I can offer what I've picked up from watching countless episodes of The Joy of Painting: for mountains, Bob almost always mixes blue, black, brown, and alizarin crimson (sometimes without the crimson). For evergreens, it's the same but without crimson and with green unless it's a winter scene (no green snow allowed haha). I've actually seen a Bob Ross 'Mountain Mix' tube of paint for sale, but that seems a little unnecessary in my opinion.
When it comes to why to not use a color straight from the tube, the answer probably stems from color theory. I'm really a novice when it comes to this, so I'd really like to hear others' take on this, but my basic understanding is that things that are farther away are lighter, cooler (bluer?), and less saturated (greyer?). Generally speaking, colors straight from the tube are too pure to appear realistic. Regarding brown, Bob sometimes does use pure van dyke for banks and trees in the foreground, but then highlights them, so it ends up not really being pure brown anyway. I wish I could do more than speculate, so I apologize if this isn't helpful: maybe mixing a black or a brown or purple instead of what comes out of the tube, has to do with how it interacts with other colors/blending with the liquid white? I hope we hear from someone with more knowledge on the subject, thank you for indulging my ramblings!
It would be really cool if there were some sort of cheat-sheet for some of the most common situations/elements.