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Doc Anderson turns up as a random encounter at campsites (the same kind that give you Ron Staples), while the Scribe turns up at encounters on the road (the same kind that give you Smiling Larry).
Riley at the cannery (do not do cannery quest.)
Ann Hargraves WNVR after rescuing guy in Trinity Tower.
Vault-Tec Rep in Rexford Hotel.
That does not qualify as Merchants/Traders.
Riley might be in the Boston merchant center, what's it called again ?
Riley is at the Cannery. You can exit and hire her, but if you do the cannery quest she ends up disabled.
If you have the UOF4P then after the cannery quest she appears at any campsite.
Tina De Luca is one that will turn a level 3 shop into a level 4 shop. Specifically for the trading emporium (the general goods merchant), along with Trader Rylee and the Vault Tec Rep.
Parker Quinn isn't normally recruitable as a settler, but if you do so with console commands, he can acts the same as Ron Staples does, but only when assigned to a trading emporium. (The code for this was copied from Ron Staples, apparently.)
I read about using intimidation on Parker Quinn but never tried it.
Parker Quinn can be made to follow you into a settlement with Intimidation 3, then assigned to a trading emporium.
No console commands needed.
https://steamcommunity.com/sharedfiles/filedetails/?id=2807083145