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I'd go for agents first. Why? Because there are plenty of good YA agents, and if you manage to get one they'll be able to get you a better offer than you'd get by subbing directly to publishers. Of course, do your research and only query good agents.
It's perfectly acceptable to query multiple agents at once. They expect this.
As for sending out actual manuscripts to multiple places, it depends on their guidelines. If an agent requests a manuscript, they'll let you know if they want an exclusive or not. A publisher, similarly, should have listed in their guidelines whether or not they accept simultaneous submissions. A lot of them don't (yet another reason why going for agents is a good choice... it'll probably be faster, since you can send out batches of queries).
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