By "Network" do you mean Domain? Using a different account login?
Each account has it's own profile. If she's logging into the Domain and her "My Documents" is set to the default location of C:\Documents and Settings\userid, then, they are located in the profile associated with the Domain account.
When she logs in locally, the "My Documents" is located in the profile for the local account.
Just an observation, but I'm very surprised that as a DA, you don't already know this.
If you want users authenticating to the Domain, then they shouldn't have local accounts. If they need Admin privileges, then they should have a local account that is used only for the "Run As" command to install, run software requiring elevated privileges.
Life's more painless for the brainless.