Since you follow users instead of subreddits, you start to know usernames a lot more than you ever did on reddit. It's cool. Because of this I learn more and more about the people on this site over time. I'll learn their interests and hobbies and opinions on different things and I'll link all those bits and pieces of information together. A couple months later I realize I know these people pretty well. This is such a weak answer. I apologize. I drank far too much last night.
If you don't mind, I'll provide some advice. In real life we tend to meet people around topics; at work, a tennis league, a gaming group, french class etc. I think the best way to use Hubski is to follow one or two people (kleinbl00 is a good one) and then to follow a number of tags. As you start seeing good content from people via those tags, follow the ones that post it. Also, I follow and unfollow people all the time and people unfollow me and follow me all the time. I don't take it personally. You should be able to follow and unfollow without feeling any sort of "pressure". But... if you are looking for people to follow right now, check out the "badges" link at the top of the page. It has some of the best content from the site. Also, the community link at the top of the page has some nice resources.
It really depends on what you like. Go to the tags page and click a tag. I'll choose drugs because....I love drugs? Anyways. If you look down the list you can see that minimum_wage seems to post a lot of content, so that would be a good choice to follow. Rinse and repeat. As you go on you get a feel for the people who's content you read and content you don't. Another great way to judge is to go into your settings and set "share-counts:" to yes. Now when you hover over a name you can see how many things you've shared by that person. If you're following someone and that number is zero, then it might be a good idea to unfollow them. If you don't follow someone and that number is 10, it would probably be a good idea to follow them. As you build your feed, you can always check out the global posts at the top and discover new stuff. Hubski gives you a myriad of ways to discover and read new content.