Set bottom cake layer, graham cracker crust side down, on a cardboard or acrylic cake disc for easier decorating, or directly onto a cake plate.
Transfer some of the chocolate buttercream to a piping bag fitted with a wide tip and pipe a thick ring of frosting around the rim of the cake.
Spread half of the chocolate ganache on top of the cake inside the ring of frosting. Transfer to the freezer for 5 minutes to set the ganache layer.
Spread half of the toasted marshmallow filling on top of the ganache layer. Gently place the next layer of cake on top of the marshmallow filling, then repeat piping a ring of chocolate buttercream, filling with the remaining ganche, chilling to set, then adding the remaining toasted marshmallow filling.
Place the final cake layer on top and frost the outside of the cake with a thin crumb coat of chocolate buttercream frosting. Transfer the whole cake to the freezer for 15-30 minutes to set up.
Remove the cake from the freezer and top with another acrylic cake disc or cardboard cake round. Frost the outside edges of the cake with the chocolate frosting, using a cake scraper to scrape the sides smooth. You may need to fill in holes with additional frosting and repeat the process of dragging the cake scraper around the cake to get a smooth finish. Place the cake back in the freezer for another 10-15 minutes.
Use a thin, sharp knife to separate the cake disc or board from the top of the cake. Spread the remaining chocolate frosting on top.
Assemble graham cracker halves, squares of Hershey's chocolate, and large marshmallows into s'mores and place them on top of the cake, if desired.
Additional graham crackers, Additional Hershey bars, Additional large marshmallows
Fill a large piping bag fitted with a large tip with wide teeth with the marshmallow fluff. Pipe the marshmallow fluff all over the top of the cake.
Use a kitchen torch to toast the marshmallow fluff and marshmallows in the s'mores decorating the top of the cake, then slice and serve.