That's basically my question. I've finished my first ambition and I got attached to a couple of my heroes that I would like each of them to create their own kingdoms now. I know I can do this for one of them using that quest mentioned above, but once I do that, will I be able to do the quest again to send another hero out on their own, or will all other heroes be stuck in that kingdom forever?

Also, will exported heroes ONLY be available for a new kingdom or will they also be available as "preset" characters for new buildings in existing kingdoms?

Thanks.

EDIT: I have another question in mind: do different ambitions have different quests or are all quests the same, just under a different ambition setting?

It may only be used once per kingdom, meaning that everyone else is "stuck".

You're only able to choose the hero as Monarch in the newly established kingdom. If you just want to save the hero's appearance as a preset, you can do so while in CAS.

I mostly fool around in my eternal kingdom doing nothing, but from what I can tell, then no. The ambitions share the same quests. But each ambition have its own sets of goals, so you'll need to consider which quests will benefit you the most as your quest points are limited.

If you forgot to save your heroes in CAS you can use the 'Carry Over Sim' function in Grim's core.

It's the same quests, but there are 71 quests in TSM and 15 quests in P&N, so you won't necessarily be doing the exact same set every kingdom. What quests appear is dependent on what heroes you have and which ones you've already done in the kingdom.

Awesome. Thanks for your replies! Chickie Teeta, does the Carry Over Sim function from Grim's Core function similarly to the Brave New World quest? I mean, if I carry over a Sim will I be able to use it as a Level 10 Monarch with previous skills retained and all?

The function is from Brave New World, I think, which is why you can only carry over one sim at a time, but it won't save their levels. It's useful for getting sims you want to keep in to the cas sim bin for use as future heroes.
What you do once you've carried your sim over is go in to your saves folder, open the CO folder, remove the file from there, rename it using the format 'firstname_secondname' and drop the file in to the saved sims folder.
You can always use Grim's core to add the lvls back to the sim.
It's handy for saving heroes you forgot to save, or didn't think were worth saving at the time you dropped them in to the world. It's also handy for saving NPCs you like, especially if you've taken time to make them over in CAS, and also for aging up your sim's kids and saving the adult versions of them to the bin.
I find the kid saving handy for a generational type game where the eldest Prince will be Monarch in the next kingdom and any brothers or sisters will perhaps be other heroes. That way I can play a generational type game without worrying about overusing any one kingdom.