Affiliate networks offer you access to multiple (and by multiple, we mean hundreds if not thousands) of individual affiliate programs. They basically work by simplifying the signup process - instead of applying to become an affiliate for a each product you want to promote, you simply apply to join the network and instantly have access to hundreds of different affiliate offers.
Be sure to check what kind of customer support you can expect from your affiliate program once you have signed up. Do your research online and if possible, speak to other sellers using the program to get their thoughts. Can you speak to someone via phone or Skype or do you have to wait 72 hours for email responses? Be clear on this because trust me, you will need support at one point or another.