@wanderlave so far in my playthrough, the best options for a path of character recruiting is as follows
Throne - Steal % (Day) / Knockout Level Based (Night)
Sub Job - Undetermined (I have Dancer atm for Dagger toss)
Starting with throne also lets you get the Inventor Job class right near her starting point, which requires you gather items to learn skills but once you do, the Inactive Battle Skills on this hidden job class are the ONLY thing you can use during the other characters story from your main game, which makes them solid gold for character collecting. I assume any hidden class does this, but you won't be finding any others this early in the game, its suicide to try.
Not to mention Throne rocks and will likely be completely OP and own the whole battlefield due to being able to act twice in one turn with her Latent Ability, and her story is great.
Osvald - Info Gathering % (Day) / Forced Steal or Mug (Night)
Sub Job - Thief (Helpful for Mug weaknesses)
Temenos - Follow (NPC Joins Battle - Day) / Forced Info Gathering (Night)
Sub Job - Scholar (Overpowered and broken forced intel gathering using Elemental Barrage and his Latent Power to make any hit a weakness)
Cassti - Info Gather (Day) - Sooth (Night, also Knockout)
Sub Job -
Who cares
Cassti - gets a skill as her FIRST Inactive Battle Skills (that others can learn) to restore 30% of HP and MP - this completely breaks the Night Mugging and Info Gathering with Osvald and Temenos by letting you refill your gauges between battles with townsfolk to shake them down for everything in a town that you couldn't steal, beg, or bribe out of their hands with other characters as you get them.
Just remember not to loot a town that characters start in until you do their first chapter story because they always start without your party and at level 1 regardless how powerful you are.
You steal all their starting gear, they have no money...its gonna be a rough chapter
Next recommendation would be
Agnea - Follow (Day) / Entreat or beg lol (Night)
Sub Class - i find her and the Thief go well together although it doesn't give either many more weapon options.
Hikari - Learn Skill (day) - Bribe (Night)
Sub Class - Undetermined
This guys a monster of an attacker and I've found no other class similar to the Warrior yet to give him a fair chance...I'm also still building up his levels but so far he doesn't have anything except bribe that gives to the overall map cleaning functionality except bribe, and personally I rather beat the shit out of the townsfolk than pay them
I'm sure he'll likely be in my main party after I clean up the entire world map, but for now he's not too important.
I still have 2 more characters and main classes to go, as well as 3 more hidden jobs and most of their secondary EX skills to checkout, but for starting the game I would suggest those 4 characters first, maybe pit stopping to grab Agnea since she's pretty useful on your way to Cassti.
I want to add that this game has the most fleshed out NPC interactions in ANY RPG I've ever come across to date, you can battle almost all of them and they even talk, steal from them and get caught, multitude of weapons and weaknesses to the point of scary and each of them has a visible strength of the possibility they kick your ass...as well as have them join you in battle and have such a versatile range of skill uses it may be more than your characters can even learn themselves (except Hikari who can learn one from all of them, up to 5 at one time)
The amount of laid out work into the towns themselves is more effort than you see in most full fledged RPG games for character buildup these days...its a fucking mind job, it makes Gau's skill set from FFVI look simplistic and it reminds you what a JRPG should actually be like...I doubt I'll EVER try every NPC skill or learned skill by Hikari and probably rely on guides to find the best characters to follow me into the depths of hell and teach me the most OP skills for Hikari since I don't have that level of patience anymore.
I do have to say, Square, Acquire...we salute you for this gem among the debris of what used to be a solid genre
EDIT:
Info Gather = Find Hidden Items / Solve Sub Quests