Tina won't talk if you get her to a settlement. You have to keep insulting Bobby and make him attack you during the Dependency quest, then kill him. This is the only way to get Tina to actually come to your settlement, otherwise she remains bugged and says she's coming to a settlement but never actually leaves the Vault. By doing this she'll cease to have dialog though. Bobby isn't supposed to be recruitable.
I believe that Sheffield and Tina De Luca are the only non-vendor recruitable settlers that are named, aside from the Concord settlers and some of the settlers that are defaulted to certain settlements like the Abernathy, Finch, and Warwick families. There's also synth Shaun if you want to count that.
As far as the Level 4 vendors are concerned -
Vault-Tec Rep, general store
Trader Rylee, general store
Anne Hargraves, clothing stand
The Scribe, armor stand
Smiling Larry, weapons stand
Ron Staples, bartender
Doc Andersen, medical station
Holt Combes in Vault 81 is supposed to be recruitable as a general store merchant, but the dialog convincing his wife to leave him is bugged and the option to recruit him almost never becomes available.