Most people do it poorly. But in early stage companies, the people you hire (and fire) to form your executive team are critical to the success and often the survival of your business. Any early stage CEO must read Marc Andreessen's post Hiring, managing, promoting, and firing executives on this topic.
Marc nails it as he discusses how and who to look to hire, how you know if they are right for the role, how you can tell if they are succeeding, and how you know when it's time to pull the plug.
As Marc suggests, getting it right 50% of the time ranks up there as a best practice result. So figuring out if you have done it right, earlier rather than later, is essential. His post offers a checklist of thoughts before you make (or keep) that big mistake.