I think you should take it one step at a time. Don't worry about too many frills in the UI, you can always add to it more later. Keep in mind how you want it to look, and afterwards you can create better looking styles etc. in Blend.
I personally use Visual Studio for most of my development, even the UI. I use blend for creating templates or styles mostly. It used to be that blend was superior to Visual Studio in the designer support, but with VS2012 it has gotten quite good. Also, Blend has a learning curve, it would take some time to get used to. Since you are new, I would suggest not overcomplicating things for you.
The number one thing you need to know about WPF vs. Winforms is complete separation of UI/App logic. It is often much easier to create "ViewModels" with properties and bind those properties to the GUI. If you try to get too involved manipulating GUI elements from code, you'll start digging yourself into a deep hole. The GUI should be databindings, triggers, behaviors, templates, etc.