With your Windows Live program open, click the “Accounts” tab on the ribbon and then select “Properties”
In your Properties window choose the “Servers” tab and make sure that the box next to “My server requires authentication” is checked. Once it is check click the “Settings…” button next to it and make sure that “Use the same settings as my incoming mail server” is selected. Then click “Apply” and then “OK” to close that window. Then, back in your Properties window select the “Advanced” tab.
Under the Advanced tab, make sure your “Outgoing mail (SMTP)” is set to 587.
Click Apply and then Ok to close this window and you should be good to go!