I would suggest that you set up an email account for your husband in hotmail. This would be best practice considering he will be using it for job applications.
In Outlook Express go through the process for creating a new account using the new hotmail account.
One thing of note here though. When using Outlook or Outlook Express files cannot be shared on user accounts. So if you open your husbands email in your XP account, when your husband logs in to his XP account, he will not recieve the email as it has already been opened in your XP account.