That won't work easily with Outlook if you only want encrypt a single folder, as all mail within an account is stored in a single file. Thunderbird however has a separate file for each folder, so you could encrypt just a single folder using Windows encryption and Thunderbird.
I can't remember whether Outlook Express uses a single file or not.
Be aware that XP Home does not have file encryption built in.
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Remind me to change my signature to something more interesting someday