Databases first. Understanding, building, normalizing, writing t-sql is probably going to give you more milage than any of the other technologies you listed.

.Net - The future is with .Net, the faster you jump on board, the more opportunity you will have to achieve your goals. VB6 is good, and there is a lot out there, but it will be dying off, and there are plenty of VB6 people out there right now that can support the stuff that is already written. VB6 would not be a 'only' skill type of language for working in the future.