Check if you have tomcat-users.xml.new file; if not, check if tomcat-users.xml (normally shipped with Tomcat) is present in the Tomcat's conf directory.
If the file is present, then change in server.xml file, the occurence of tomcat-users.xml.new to tomcat-users.xml and restart Tomcat. This should help.
Both tomcat-users.xml & server.xml should be under
C:\Program Files\Apache Software Foundation\Tomcat 5.0\conf directory.