No she will not but taxed. She is exempt because she is "settling" in for the first time as a newcomer.
They understand that immigrants have stuff from home to bring to Canada when they arrive.
However, she will need to fill out these forms
Fill out only this one if you don't have that much to declare or categorize your items (B4):
http://www.cbsa-asfc.gc.ca/publications/forms-formulaires/b4-eng.pdf
If you need more space than can fit on the B4 then you will also need to write the rest over to the (B4A):
http://www.cbsa-asfc.gc.ca/publications/forms-formulaires/b4a.pdf
If you have goods to follow you will need to print out another B4 form but instead on this one you will just check off "Goods to Follow".
To learn more about the B4 and B4A forms or declaring things you can search the forum here. There are many helpful threads.
It is needed for her to both declare her goods when she "lands" to become a PR at the airport and also that she declare any goods that will follow later, like through mail, etc. Those forms should help you out. And this form here explains what she can bring duty free:
http://cbsa-asfc.gc.ca/publications/dm-md/d2/d2-2-1-eng.pdf
P.S. You can also find many helpful things about the CBSA site.
Good luck with everything.
