<p>For a newcomer to .NET Web Development and programming in general, who chooses C# as there preferred language?</p>

<p>Is it better to learn C# first, without trying to apply it to web development? It seems most literature for C# uses Console or Windows Forms as a learning platform. So would that be the best direction?</p>

<p>Or should you practice in web development and try to learn C# alongside?</p>

You need to understand the fundamentals of C# in order to develop anything useful, be it an ASP.NET website, windows client or web service.
I would start with some good tutorials around the basics of types, classes, methods, events and so on to get to grips with C#. C# Station has some good introductory tutorials
here
.
To develop web specific skills, start with HTML and CSS.
Then look at how the ASP.NET platform integrates both the C# (application code) and the HTML and CSS (presentational code).
And good luck!