If she is still under 30 (I am doubting that if she was teaching in 1999), she could apply for a working holiday at
http://www.whpcanada.org.au/introduction.shtml It's not permanent but would allow a 2 year open work permit which would help making connections and getting to the point of applying for PR.
Was she a college teacher? Then she could apply as a skilled worker under NOC 4131. Her experience points as a teacher will still count as all skilled jobs count, not just the 38 most wanted so she does have enough points. She would however have to find an angle to qualify her to apply under some category. If she did not have at least 1 year experience in any of the 38 most wanted jobs, she can not apply under category 1. If you are in Canada, maybe you can help arrange a job for her, arranged employment. That would get her in under category 2. If she comes on a student visa and stays in Canada for 12 months or more, she can apply as a skilled worker under category 3. It's all explained here:
http://www.cic.gc.ca/english/information/applications/skilled.asp and here:
http://www.cic.gc.ca/english/immigrate/skilled/apply-who.aspShe can also try the self assessment for Quebec skilled worker, see
http://www.form.services.micc.gouv.qc.ca/epi/index.jsp?languageCode=en