Lee Markum has a starting point for DBAs in a new role:
You’ve just been hired into a DBA role at a new company, or you’ve been given the DBA keys at your current company. Maybe you’re a SysAdmin and your boss has informed you that you are now supposed to manage the SQL Servers as well as everything else on your plate. In any of these situations, you may have some confidence in your skills, but especially in the case of being a new hire, you have absolutely no true idea of what you’re walking into.
In these scenarios, where do you start? Start with these four areas.
Click through for the four areas. I completely agree with Lee on these for DBAs, including the order.