Drive east from Cangas de Onís into the park toward Covadonga — a sanctuary built into a cliff face above a river gorge that has been a place of pilgrimage since the eighth century. The basilica is pink and improbable and entirely out of scale with the landscape around it, which is precisely what makes it worth seeing. The holy cave built into the cliff below the basilica contains a small chapel and a spring and the atmosphere of somewhere that people have been coming to with serious intent for over a thousand years.
Do not spend too long at Covadonga itself. The real objective is above it.
The road from Covadonga climbs through forest and then above the treeline to the Lagos de Covadonga — two glacial lakes sitting in a high mountain bowl at around 1,100 meters. Lago Enol and Lago Ercina are connected by a short path and surrounded by karst limestone terrain that looks nothing like the green Asturian valleys below. The peaks of the western massif rise above the lakes on three sides. On a clear day the reflection of the rock faces in the water is the kind of image that does not require any photographic skill to capture well.
This is your first proper mountain moment of the itinerary. Take it slowly.
Practical note: between late June and mid September the road to the lakes is closed to private vehicles due to congestion. A shuttle bus runs from Covadonga and takes about twenty minutes. Outside peak season you can drive directly. Check current access conditions before the day.