You mean a prestige class? Yes, I would be most interested to figure out how to do this as well... When I mod I often require my NPCs to have such classes.
The problem is this:
I don't believe it would be possible to get the game to just put it on a list with other classes in the actual game. Editing would have to be done using the editor and Leto.
You could also write a script that would give the character a custom item at level up, one that might cast spells or (if equipped, like a ring) enhance abilities. I've seen it done before, but I know little about scripting. I just know that it has something to do with the OnLevelUp script of the module. What I would do, if you want to go through the trouble, is to download a HAK and examine the scripts. That should give you a general idea of what to do.
Hopefully, someone else is more of a script person than an idea person and will know exactly what to do.. I just do what I have to do by looking at things I see and using that as a blueprint.
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