C# is very similar to Java in syntax, but not really in style.
Here is a link to several coding styles and it includes the suggested .net style.
coding guidelines
There is some additional language elements, like Properties (think getters and setters) and the ability to overload operators. In general you don't need all of these things to get work done, but you do need to think about how they could be used.
The newer features in the language like LINQ are just something you'll have to pick up over time. Most C# programmers who have been working in the language for years don't really use LINQ outside of some experimentation. Hopefully this will change.
As for .NET, well it's huge, just like the JAVA API, and picking it up is really a long labor of many years. You can become quite good with sections of it though and be super productive very quickly. My suggestions would be to focus on System.IO, System.XML, and System.Data, those seems to be the libraries that I see used most.