Much of the rural portions of the Trans Canada Trail (TCT) are really rough and more suitable for full-suspension mountain bikes and hiking. In some parts they are sections of rails-to-trails, the well maintained ones are gravel paths, the ones that are not are chockfull of roots and rocks. In urban areas, they are often paved, and offer a good way in and out of the cities. Many parts of the TCT are still under development or even still to be determined.
The Trans Canada Highway (TCH) is very much automobile-centred, in most of western Canada it is OK for cycling, in central and eastern Canada it is often too busy and there are better alternatives. Cycling the TCH all the way would be a noisy, fume-filled route, sometimes convenient but not always the best.
My recommendation for a cross-Canada route starting from Vancouver would be:
BC: Hwy 7 out to Hope, TCH (Hwy 1) all the way to the Alberta Border and Calgary
AB: from Calgary find your way out to Hwy 9 via Drumheller to the Saskatchewan border (Alsask)
SK: from Alsask, highways 7, 15, 44, 19, 42, 2 to Moose Jaw; THC to Regina; highways 33 and 13 to the Manitoba border;
MB: Hwy 2 aka "Red Coat Trail" to Winnipeg; TCH (Hwy1) to the Ontario border. Note: the roads in Manitoba are the worst you'll encounter, none of them have shoulders. Hwy 2 likely has less traffic than the THC or the Yellowhead Highway (Hwy 16)
ON: with its good and bad portions, Hwy 17 all the way to Petawawa; small county roads into Ottawa (message me if you want exact details)
QC: from Ottawa, cross the river and follow Route Verte (RV) 1 to Montreal, RV 5 to Quebec City, cross ferry to Lévis and back on RV 1 to Rivière-du-Loup (for inland route or Mont Joli—Matapédia for coastal route.
NB: inland route – at Rivière-du-Loup QC, take the TCT aka "Petit-Temis" trail to Edmunston NB, take Hwy 105 to Fredericton, 112 to Moncton; 134 to Shediac.
Coastal route - enter NB at Campbellton; Hwy 134/11 to Shediac; coastal road from Shediac to the Confederation Bridge, bridge shuttle to PEI.
PE: The Confederation Trail and associated rail trails can take you across the island from Borden to Wood Island; Wood island-Caribou ferry to Nova Scotia
NS: Hwy 4/104 to North Sydney for the Newfoundland ferry. Check
ferry schedule to make sure your arrival is synched with a sailing day
NL: Long Way – ferry to Port-aux-Basques TCH to St. John's;
Short Way – ferry to Placentia, highways 100, 13, 10 to St. John's