you just choose one, and apply. You should probably pick one that fits your zanpakuto or your skills. Hell. If you do really well in RP's, you may be selected as an emergency replcement captain. like if one dies or quits. And there's also a possibility that you may be sent to other squads by your captain, like how Kaien used to be a squad 5 member, and eventually joined squad 13. actually, I believe that there are still vacancies for captains, so you can actually become a captain while you still have the chance. you just have to apply on the "captaincy test" on the main forum page.
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