Honestly, I would say you'll have a much easier time designing a simple user interface in VB.NET/C# than you will in PHP. If you aren't familiar with HTML, you'll be lost with PHP. At least in Visual Studio you can use the Visual Designer to create your page. I've been in software development for over 15 years, so I'm not talking out my a$$ 
There are a billion VB.NET examples on the web and MSDN is probably the best programming resource out there (Microsoft Learn: Build skills that open doors in your career).