Hi,
Considering the fact that .net is a massive collection of classes, structs, interfaces, methods etc what would be the correct and appropriate approach to get started with and understand the fundamentals of the framework.
Bearing in mind the two facts that there is no substitute for experience and that there is no limit to learning.
Many Thanks.
Start off by picking one of the .Net languages to learn. I would personally go for C# as being the mainstay of .Net development. Then just go and code something, like problems from Project Euler.
Once you've mastered the basics of the language (like the data types, language constructs and so forth) then it is an appropriate time to start learning one or more of the .Net frameworks. Here you just pick whatever you're interested in, be it WPF for desktop development, ASP.NET/ASP.NET MVC for Web development, WCF, etc.
Language first, libraries second.
Learn C instead.
No, just kidding. Have you got any experience in other programming languages and if so which one(s)? The correct approach for you will be largely dependent on that. If you have any experience with Java you should try C#. If VB try VB.Net. If Python try IronPython. If Ruby try IronRuby.
It depends on your persona. Some people like the book approach - find something like the 70-536 syllabus, and start reading. Personally, I'm more "hands on" - pick a technology (for example ASP.NET MVC) and a language (usually C# or VB) and start trying things. When you get stuck, or unsure, look here (search first), then ask ;-p
Note that the language is in many ways secondary, but people tend to get religious about it...
You don't need to learn the whole framework, pick a good book start learning it. While learning you'll have problems, and you'll see other's code which will help you. Try to get a book with lots of examples.
You just learn what you need example if you want to develop web applications you won't go and learn how to make WPF or windows forms application but you will need to learn about ASP.NET
I think the best way to learn .NET is to write applications (doesn't have to be big or complicated) that .NET was designed to do, like data-driven web app that's designed using components instead of writing html directly, desktop application that consumes Web Services, services that's interoperable with other platforms etc.. that sort of things.
Something like a Twitter client would be something fun to start. You can start simple, and gradually add features as you learn more about .NET. As you read and write in C#, you'll eventually pick up the language.
Where to begin largely depends on your learning style. Personally, I like to take stock of the tools available to me before I tackle a problem. I like to know what's in the toolbox and get a feel for what each tool does. Others prefer to dive into a problem and crack open the toolbox only once they know what type of tool they're looking for. This, to me, is slower and increases the likelihood of picking the wrong tool.
If you're like me, I'd recommend (like Marc Gravell) the 70-536 training guide. The examples are probably too trivial to apply to the real world, but that's not the point. It's purpose is to give you a guided tour of the toolbox. Start here to get your overview of the core framework and then move on to one of the books (or online tutorials) that'll guide you through leveraging parts the framework to accomplish something practical.
Like others have said, I'd say first, pick a language of the .Net framework. After you have decided on a language, decide on what type of applications you want to develop. .Net has portals for learning each application type.
Windows Clients (WinForms or WPF) - http://windowsclient.net/
Web Clients (ASP.Net or ASP.Net MVC) - http://asp.net/
Silverlight/RIA applications - http://www.silverlight.net/
Each of those sites have specifically targeted tutorials that'll help you learn the language as well as how to apply them into the types of applications you want to develop.