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Well, can they?

E.g. Could a Space Marine Captain and Librarian join a Tactical Squad together?

I did this in my last game and am wondering if its legal. I actually turned out to be a serious disadvantage though.

Yes.

Editing to add:
iirc it's page 48 of the main rules.

Page 48, IC rules. Everything you could ever want to know is in there. Learn em, love em.

Yeah, I had read that page. Two ICs can join and an IC can join a unit. My scenario wasn't mentioned, but seems reasonable.

Essentially, IC's are given permission to join units. Nothing in the rules suggests that having an IC already joined changes that permission.

So yes, perfectly legal.

insaniak wrote:IC's are given permission to join units. Nothing in the rules suggests that having an IC already joined changes that permission.

As simple as that, really. It might not always be the best move to put all your expensive ICs in the same unit, but nothing limits IC+unit to one IC only. The IC rules even explicitly state situations where an IC may not join a unit.