As stated by Jon Skeet, this is not available in the Webclient not HttpWebRequest classes.
However, if you have control of the server, that receives the upload; perhaps you could upload small chunks of the file using WebClient, and have the server assemble the chunks when all has been received. Then it would be somewhat easier for you to make a Pause/resume functionality.
If you do not have control of the server, you will need to use an API that gives you mere control, and subsequently gives you more stuff to worry about. And even then, the server might give you a time-out if you pause for too long.