You're off topic for this forum, which is dedicated to Windows Live OneCare.
Are you using Windows Live Custom Domains - now called, Windows Live Admin Center?
If so, and you added a new email user to the account, this mail should be available via Windows Live Hotmail on the web or Windows Live Mail.
If that isn't working, contact support for Windows Live Admin Center -
https://support.live.com/eform.aspx?productKey=wldomains&page=wlsupport_home_options_form_byemail&ct=eformts&mkt=en-us
If you simply created a new LiveID using an email address for your domain and are not using Windows Live Admin Center to host the domain, Windows Live Mail would get the mail for that account from your mail host, it isn't a Hotmail account simply because you made it a LiveID. When you create a new LiveID using an email address that is not a Hotmail account, it does not provide you with a Hotmail account automatically.
-steve
