The short answer is:
- Yes you can.
- Ini files are loaded on the startup of Unreal Engine. I think they are validated on assignment.
- No. If you want to have additional .ini files you have to create them yourself. (not only that but I think you need to have your categories added inside)
Here is the documentation if you need more in-depth answers.
P.S. You can also check this Config Files, Read & Write to Config Files | Unreal Engine Community Wiki for particular exmples.