This book is intended for the complete novice who's never programmed in any language before. It works slowly through the basics and explains simple syntax, building forms, handling events, working with variables, and so forth.
It doesn't get to anything too terribly advanced and unfortunately XNA is pretty advanced.
When you're done with this book, however, you should be ready to read most of the other books about C# programming including the XNA books. Some of them can still move pretty fast in their topics so they can still be pretty hard but you should be able to read one of their examples and say to yourself things like, "Here he's creating a new Pen object, this using statement is to free resources, and here's he's making a List that can hold only Drawable objects."
Programming in .NET it a truly enormous topic whether you want to go into database programming, ASP.NET, or XNA so you'll have a lot more to do, but I think this book is a good first step.
Good luck! And when you build some interesting programs, let me know and I'll post them or link to your site so others can see what you're doing with C#.