WElllllll.....ask BA if they will just transfer you w/o any fees if you miss the earlier flight.
Your flight fom Vancouver could be late....very heavy air traffic at LHR...I have often been in a holding pattern for quite a while before landing.
The infamous Terminal 5 is at quite a distance from Terminal 3. I don't know the actual transfer time from 5 to 3 but you might find some infomation on the Heathrow web site. Terminal 5 is the one that just had all the baggage problems this week.
Since you are arriving from Canada and transferring to a domestic flight, you will also have to go though immigration.
You may have no problem but then again.......I don't like drama when arriving half asleep so I would go for the later flight but that's just me!!! I go though Terminal 3 all the time and it is very busy
and big! (and I fly off season). There are lots of shops and places to eat at T. 3 to keep you busy.