I would suggest trying to use Blender is going to lead to you not having a very good time. I don't know that the KOTORBlender script is up to the task of exporting animations in the proper format. It's a pain in the ass trying to get Max to do it. Maybe you could get a workable solution with some manual editing of the ASCII, but I'd suggest experimenting with something simple first to see how it goes.
Be aware that, generally speaking, you can't just add "new" animations. The game has a hard-coded limit on the specific animations it will accept for combat and so forth. What exactly are you wanting to accomplish?