There is one thing that nobody ever thinks about, with either Outlook Express 6, Windows Mail or Windows Live Mail.
That is, that every email folder has to load into RAM memory in order to open. If a folder gets too large to fit into ram, like the Sent Items folder, a failure to function will occur.
I had one customer who could receive mail but not send mail. I had set up her email client myself so I knew it was done right and worked perfect when it was set up.
But one day she could not send mail. Her ISP tech support was no help at all, so she called me.
To make the story shorter, I found that her "Sent Items" folder had never been cleaned out in several years. It was so large that it could not be loaded into her available RAM.
I emptied that folder and everything was working again.
Now she knows, to empty her sent items folder as well as her Deleted Items folder on a regular schedule.
Also, sometimes an ISP will change things like email ports, without notifying their customers.
First, check with the email provider to make sure all port settings, etc., are set properly.
Good Luck,