Multiple screens are a bit of a problem and it does not have a built in, nicely wrraped way to handle them, but with some math and SystemParameters you can get it done.
If you position your window at position (0,0) that would be the top left corner of you primary screen. So in order to make your window appear in the center of that screen use:
this.Left = (SystemParameters.PrimaryScreenWidth / 2) - (this.ActualWidth / 2);
this.Top = (SystemParameters.PrimaryScreenHeight / 2) - (this.ActualHeight / 2);
The basic idea is simple enough so no need to explain.
Note this code is for C#, but i am sure VB has something similar.
Also note you should use the ActualWidth\ActualHeight property and not the Width\Height property as it could hold a NaN value.
Good luck.