There are buses every hour from the Dundas and Bay depot. These alternative between GRAYHOUND and TRAILWAYS and a local firm. It's a pooled service so doesn't really matter who you book it with. US INS will require a round trip ticket -- you can cash in the return at the depot. From the downtown Buffalo depot, its a $30 cab ride to the airport, or a $1.50 city bus ride.
Expect an hour to be processed at the border. You must get off the bus with your carry-on, then await the dog to sniff you out, and after that each person is interviewed and entry granted, or not.
It is non-stop to Niagara Falls where most people get off -- during tourist season at least -- and then on to Erie and the Peace Bridge crossing. About two hours to the bridge from downtown Toronto with the Niagara stop.
VIA also runs a daily train leaving Toronto Union Station at 8:30a and rolling into Buffalo station -- nearby bus depot -- at 1:10p. Again, you must generally buy a return ticket.