Nearby the Firelink Shrine you should probably have spotted some skeleton enemies and a small graveyard. To the left of this graveyard, near the cliff, there is a ramp that leads to (in my opinion) one of the most annoying areas of the game: the Catacombs and, going further, the Tomb of the Giants.
To acquire the Rite of Kindling you'll have to beat the boss Pinwheel that is located at the end of the Catacombs and guard the entrance to the Tomb of the Giants. Although the Catacombs area may be hard for low-level players, it is worth it to push your way through at least until you beat Pinwheel and get this trophy because with it you'll be granted the power to kindle your bonfire flames even further, allowing you to get up to 20 Estus Flasks from any bonfire you do it with. However I highly recommend you turn back and leave the area once you have beaten him and leave the Tomb of the Giants area for later on.