You just need to locate the store folder and back of all the files, its a while since I have last had to back up outlook express but you will find a folder. In XP its very well hidden and you need to enable hidden folders. If you ho into outlook express, click on tools and accounts (I think) you should see a section which says maintance, in there will be the store location. Navigate to that and backup all the files. You may also want to back up the contents as a CSV file.
I am sure google will have a more specific answer.
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Backing up e-mails new
Backing up e-mails new