I think (think being the key word there not know) that once you enter your past work history and school information you'll see profiles for people you might know. That's how I've connected to past coworkers. If I do a search for companies I used to work I don't see them...just generic information on them. But, I get notices telling me I might know someone when new people sign up.
At least I think that's how I've connected to some people...I know, I'm not much help. What I'm trying to say is enter all your information and see what happens.