Appropriate Store: Trading Emporium
Population Demand: N/A

Vault-Tec Rep can be found at Goodneighbor at the Rexford Hotel on the second floor inside one of the apartments.


How to get: Just simply talk to him, and ask him to go to the sanctuary, then go to the sanctuary speak to him again and ask him if he wants a job.

Appropriate Store: Trading Emporium
Population Demand: N/A

Holt Combes can be found at Vault 81 in the depot.


How to get: Talking to his wife about how he’s not helping with the store involves a persuasion check that I fail most of the time, even though I have 10 Charisma, a +3 CHA dress and Level 2 Lady Killer. There could be a special condition that has to be met in order to succeed at this conversation, but I haven’t found it yet.

Appropriate Store: Trading Emporium
Population Demand: N/A

Rylee can be found at Longneck Lukowski's cannery


How to get: Talk to her, ask her question about stuff, eventually you will have the option to recruit her.

Appropriate Store: Clothing Emporium
Population Demand: N/A

Anne Hargraves can be found inside WRVR Broadcast Station


How to get: I am not sure, but there is some theories saying that it is recommended that you should rescue Rex Goodman before interacting with Anne, however if you have not then either Anne will offer you a quest to rescue him, or you will just be able to recruit her.

Now the rest are random encounters, but most of these people hang around a specific spot, but it's random, in your first save you might find a doctor at that spot, but on your other save there might be a cook so you really can't tell who is gonna be there.

Some spots might also be randomly generated, as in you need to do something to trigger the event to encounter one of the legendary merchants.

What I recommend is that once you recruited for example the doctor at Spot #1 is that you leave that zone and come back to it, and that cook should be there aswell available to be recruited.

It's near the Mass Fusion Containment Shed next to a parking lot there is two NPC and one merchant you can recruit.

Possible merchant that can spawn -
Ron Staples — Food & Drink Specialist
Appropriate Store: Restaurant
Population Demand: 20

Doc Anderson — Clinic Specialist
Appropriate Store: Surgery Center
Population Demand: 20

So this one might be a little difficult and a bit time consuming for some, but I will tell you step by step what to do.

Step 1 -
Sleep in any settlements for 3 days(72 hours), preferably somewhere that is a bit far from Med-Tek Research Center, make sure to make a save/quicksave after you have slept 72 hours!


Step 2 -
Fast travel to Med-Tek Research center, wait a few seconds and you should see someone walking down or up the road, it is randomly generated. Sometimes it is just a caravan trader or a patrol, and if you're lucky enough it could be a legendary merchant.


Step 3 -
If you somehow have not encountered a merchant yet, instead of waiting 72 hours, what you can easily do is just load the quicksave you made from right after sleeping 72 hours and just fast travel to Med-Tek Research.

Possible merchant that can spawn -
Smiling Larry — Weapons Specialist
Appropriate Store: Weapons Emporium
Population Demand: 30

The Scribe — Armor Specialist
Appropriate Store: Armor Emporium
Population Demand: 10

#1
Question: Whenever I go to one of the spots, they are not there, what did I do wrong?

Answer: Well first you got to make sure you have enough settlers, atleast 30 should be enough as it is the average you need. Also make sure to quicksave somewhere not soo far from the spot so if that person didn't appear just reload to your last save and keep going to that spot till that person is there.

#2
Question: I can't get more than twenty settlers at one place, what do I do?

Answer: It is simple, just assign a settler to supply line to another settlement, it should merge and help you get to 30 easily.

#3

Question: I can't assign a level 4 settler to a shop, what's wrong?

Answer: Well this is a common problem, most of the level 4 settlers won't show up at the settlement you sent them to, even if they met up, they won't do what you're assigning them to do. Luckily thanks to Silva, he found a temporary solution till the patch is out which should solve this all hopefully.

If the level 4 settler is at your settlement but won't follow your orders, just open your console and click on that person and type this in the console.
setpv bCommandable 1
setpv bAllowMove 1
setpv bAllowCaravan 1
Fast travel far away and come back and you should be able to assign them.