Place a cake layer on a cake plate or pedestal. Pipe a border of buttercream along the perimeter of the cake to prevent filling from peeking out of the sides. Using a spiral motion from the outside in, pipe a third of the filling on top and inside the buttercream border. Repeat steps with the remaining cake layers and filling, ending with a layer of filling on top. Chill cake in the freezer for 1 hour.
Once chilled and solid, frost the cake with the buttercream--this will act as the crumb coat. Chill cake in the freezer for another 30 minutes to set the buttercream. Remove the cake from the freezer and frost it with a final layer of buttercream. Return the cake to the freezer while you make the ganache.
Make the ganache by placing the chocolate in a medium bowl. Pour the heavy cream into a glass measuring cup, and heat in the microwave until it starts to boil. Pour hot cream over the chocolate, cover with plastic wrap, and allow it to sit for a few minutes. Remove the plastic wrap and stir until smooth.
Using a small spoon, carefully ladle the ganache along the edges of the cake, allowing the ganache to drip down the sides.** Once the sides are done, pour a few tablespoons of the ganache into the center of the cake, and use an offset spatula to fill in the top of the cake.
Decorate the cake with homemade s'mores, toasted marshmallows, chocolate, and leftover chocolate buttercream. Slice, serve, and enjoy!
Cake will keep covered in the refrigerator for up to 5 days.