Yeah redxlaser is right, if you ask them for any supplies because your helping them, or to teach you anything while you have an active mission with them, then it nulls the mission. I believe it stays in your (M)ission list also, which can be annoying.
Once you complete the mission for an NPC, say you need no payment, then they will teach you anything at 100% chance. Some of the missions lines are also not complete, so once you do a couple they start saying “someone forgot to code this mission,” or something like that.
There was someone who was working, or laid out plans to work on the NPC code, but I dunno what ever happened with that. I think they were trying to do it over their school’s Winter break, and probably had to go back to working on school stuff, but I’m not really sure about that… I just remember seeing a thread about it on the old forum(smf) before we moved over to this forum(discourse).
Edit: maybe it was just the bases mod that was planned that I was thinking of, This was the thread I was thinking of.