Start off with just the basics, but then add bits of functionality to it.
A simple yet complex program could be software for an ATM (it's generally a very good practice problem and i've seen it in most programming classes i've taken).
Start off with the functions (withdrawal, deposit, account balance, etc...) and then expand it. Decide how you would deal with multiple customers. Look at integrating databases. That's what is going to get you places.
If money's not your thing, code an inventory system. The biggest issue in business programming is not so much the program itself (as you said, you know the syntax), it's how you store the data and the interoperability of that data between different programs, OS's, and networks.
Get acquainted with coding a "front end" which you probably could pull off the top of your head, but you really need to sit down and plan out a back end. Chances are you wouldn't be doing all these jobs in one position, but having a level of comfort with both is definitely a stepping stone in the right direction.
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I'm sure you've done this already but...
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