I don't believe you'd have any problems adding lots of extra skeleton nodes, but what you won't be able to do is have them recognized as attachment points for anything. There's no known way of defining an extra slot for mesh replacement.
Take rings for example. There are mods that allow unlimited rings, but the engine allows only two to show, and nobody has been able to change that, even though the digits of the hand are all already present in the skeleton. Just having a location isn't enough.