Well, basically you've got to think about the nature of client side programming, and server side programming. PHP, being server side, is not going to be able to do anything on the client machine... however, once the client sends something to it, then you can do a million and one things with it.
Basically, the client machine that has the camera will have to function like a server. It will need to wait and monitor some port for a request to take a picture. You could send that request using PHP, but the magic would be getting the client machine to recognize and respond to the command. Then, once you've passed the command to the client machine, the VB program needs to be able to 1) take the picture, 2) connect to the server, and upload the image. Step 2 could be as easy as telling it to simply use http protocols to post the image to the script... or you could use ftp.
Either way, the whole thing isn't going to be done using PHP alone. I think the trickiest thing would be getting the client machine to respond to a request to take a picture and upload it. Everything else is pretty straight forward.