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Where in the scenario file can I find the line(s) that dictate what leader names/portraits will be associated with a given country?

I only know for modern games. There is a file Leaders2020.csv in sandbox. You gotta find the region number and the portrait number. The portraits can be found in Graphics.

I had to fix Hillary, for some reason she is there to stay in my vanilla file, while Trump is president, but for my mod i had to fix it. Anyway prolly ignore that. But damn it was confusing and going through all the portraits. Prolly an easier way.

All leaders are listed in the DEFAULT.PPLX file (in \Maps\DATA), this file is called in the .scenario file

You can add new line there, and even call them with events using event 20 in the .CSV file

exemple in the PPLX file :

With region num :
Here i'm creating a line with id 2024 (for SR1936), leader Bao Dai with pic num 595 for country id 2197 (which is Vietnam in the .cvp file)

Without region num :
This is for a 14 years old Duy Tan, emperor in 1914, id line 3134, using picture num id 3022

Then back to our events in the The Great War - 1914.CSV file to specify the id of the line i added in the .PPLX file (here is 3134 for Duy Tan), making this emperor leader of Vietnam.
picnum ids of leader are found in \Graphics\People

Hope this helps

I'd also recommend taking a look at our wiki. It has a lot of modding info: https://supremeruler.gamepedia.com/Supreme_Ruler_Wiki