How to create a simple web service application

Question

I need some advice on which technology to use for a web application that I need to create.  I'm a bit confuse by the WCF, Silverlight, Httplistener, ASP.NET, IIS and other stuff available out there.  I have the software experience for VB.NET but not for web development. 

Here's what I need to do and maybe someone will be able to send me in the right direction.  I want to create an web application with a UI with control buttons and information to return back on the UI. That application would be accessible as web page with a browser, it would run on a Windows XP computer and be accessible by remote computers. It would not be hosted by any web server mechanism but instead it would be an executable program.  Also, I would like to build the web pages with controls as easy as it is now with windows application in VS2008.

I have tried to follow a tutorial online for Silverlight but it doesn't seem to produce an executable; instead, it seem to work with IIS but I haven't figured out how to make it work.

I have the VS2008 and building the core application in VB.NET would be the language of choice for me. 

Any advice and example to show.

Thanks