After installation of Windows-8 first thing i tried is to adding email accounts to Default Metro Email App.
I have configured my Windows Live ID(My Hotmail Account) as login to my windows and it was automatically added in Email App. For Adding other email i found that we can add multiple Hotmail, Outlook mail and Gmail accounts for email app. To add any Gmail or Hotmail account we have to add our email account to People App Accounts by clicking ?Connect to? Option.
For detailed information please see video.
It is quite simple and Email app is really very impressive and clean.