Hwy 401 is the freeway you will need to use from Montreal to Kingston. There just are no other viable routes.
Once at Kingston, you can head south and take a very scenic route with a free ferry thrown in, see
http://en.wikipedia.org/wiki/Ontario_Highway_33. At the western end, you could return to the 401, but I like to follow Hwy 2 along the shore of Lake Ontario from Trenton to just East of Port Hope. Then, it's back to 401 for the crossing of Toronto, until you take the 427 South and then follow the QEW ( Queen Elizabeth Way) to Niagara Falls.
The Niagara area is wine country. See
http://wineriesofniagaraonthelake.com/ for a few ideas and a map. There is a road parallel to the QEW to the west, nestled under the Niagra Escarpment that is pleasant and will get you near a whole bunch of wineries.
If I'm around when you are due to arrive in Toronto, I might even be able to show you the route.
There is a Niagra region chartered club you could contact as well. Should have mentioned the Quinte chartered club west of Kingston as well.
Great ride, but you will likely do freeways a fair amount in Canada.