Okay, to start any project is to sit down in a quite room with the old mark I recording device (pencil and paper) and write down your requirements. Now, since you know this project will involve a a database, I suggest you start there. Write down what information you will need to capture, retrieve, and manipulate(calculate). These would include, but not limited to, name, address, tax information plus other with holding, salary or hourly, rate, and so on.
Now, once you have all the information you want to capture and have normalizied your database design, then it is time to start thinking about how you want the user to interact with each of these sections. This of course should lead you into program design and program flow, or in other words, how the user access each of these sections and how they are connected together. Once you have that planed out, then it is time to turn the computer on and start programming and once you have any problems, come back here with the problem piece of code and we will be willing to help you as best as we can.
Also, you can probably solve a lot of your questions by yourself when you use your new best friends (yahoo, google, ask, answers, bing) to search for things like vb6 ado tutorial.