Is it possible to access the serial pins or any other digital pins through the ethernet shield as a virtual serialport?
Access pins, and reading serial data, as both possible.
It would be very easy to just access it as a virtual serial port, that way I wouldn't have to worry about rewriting the vb.net code.
Start worrying. The Ethernet shield is not an extension of the serial port.
The Arduino with Ethernet shield is either a client, periodically polling a server for information, or it is a server, periodically responding to GET requests.
You most likely want the Arduino to act as a server, responding to GET requests. The GET request will convey additional information that tells the Arduino what to actually do,
That is going to require a major rewrite of the VB application.