How I can do this? First of all, go to your "My Documents\Visual Studio 2010\StartPages". There you will find a project named "StartPage" with an additional XAML file named "StartPage.xaml". This xaml page is your Start Page of the Visual Studio 2010. Remember that this is user specific file & have to deploy for all users.
Before doing anything take a backup of the same. Now open the StartPage project file which will load the xaml in your Visual Studio IDE. Modify it according to the look & feel you want. Save it & you will immediately see the effect in your startup page.
Not only this. You can also chose different XAML files for your Startup XAML page. Create a separate XAML file with your design in the same directory as mentioned above. Open your Visual Studio 2010. Go to Tools -> Options -> Environment -> Startup.
Select the "Custom Start Page" from the drop down that you have created. Hit "OK" to see it immediately in your start page. Remember that for security reason you can't change the path as this executes under the trusted privileges of the user only & also uses some references to the Visual Studio UI assemblies.