Well that is where I started > 10 years ago. I was an instructor for MS Office and HTML. I did that for a few years becoming a relative expert. I then got a job developing Access databases and learned SQL Server on my own. I then moved to a job where both Office and SQL development skills were needed learning more about the DBA aspects of SQL Server and taking on some of those responsibilities. My next job was as a DBA and that is where I am now. I think what you must always do, though, is hold a quiet respect for the MS Office world, as no one in the DBA world wants to give them the time of day, yet, management always needs an expert in MS Office, and those are the people you need to impress.
My advice:
Get a job developing, not teaching
Change jobs every couple years working with and learning from people smarter than you
Use the training budget for you company to take as many classes as you can