You can of course develop applications in VB that connect to any database, but if all you are familiar with is Access development it will likely be a rather steep learning curve.
You have to do a lot more "real programming" in VB. Although it is possible to create "bound" controls in VB, the mechanism is not very useable in any practical sense.
Therefore you need to write a lot more code to:
1. Connect to the database
2. Load data (including filling in the controls)
3. Detecting when controls are updated, and enforcing business rules
4. Updating data
Don't take this as criticism of VB on my part. Personally, I have always preferred the extra control you get in VB, but it does require a lot more raw coding, and you really have to know your stuff.
Even if you use bound grids, you will tend to want to handle the actual updates to the database yourself.
If you are new to VB, I would recommend going directly to .NET instead. There are several advantages:
1. Free development environment using Visual Studio Express (whereas if you don't already have a VB6 CD, you may have a hard time getting your hands on one)
2. A lot of built-in binding mechanisms
3. Its currently supported and will continue to be enhanced by Microsoft