Set your oven to 350°F and place a rack in the lower third. Coat every detail of the skull cake mold with baking spray that contains flour, using a pastry brush to reach the deeper grooves. This step matters more than people expect, since skipping it is the main reason cakes stick and lose their skull shape when unmolded.
Whisk the flour, both cocoas, sugar, baking soda, baking powder, and salt in one bowl. In another, whisk the buttermilk, oil, eggs, and vanilla. Combine the two, then stir in the hot coffee last. The batter will look thin, but that's exactly what gives this cake its dense, fudgy texture once baked.
Divide the batter evenly between both sides of the skull pan, filling each about three-quarters full. Bake for 40 to 45 minutes, checking with a skewer near the thickest part of the skull. Let the cakes cool in the pan for 15 minutes before turning them out onto a wire rack to cool completely.
Beat the softened butter until fluffy, then gradually add powdered sugar and a splash of heavy cream. Fold in the crushed cookies once the buttercream is smooth. This filling goes between the two skull halves, so keep it thick enough to hold everything together without oozing out the sides.
Spread the buttercream filling generously over the flat side of one cake half, then press the second half on top to form the full 3D skull shape. Insert a skewer through the base and another near the back for stability, then smooth any visible seam with an offset spatula.
Wrap the assembled cake loosely in plastic and refrigerate for at least 30 minutes. This firms up the buttercream so it won't melt or shift once the warm glaze goes on, and it makes the final glazing step far less messy.
Melt the white chocolate or candy melts with milk until smooth and pourable. Set the chilled cake on a wire rack over a sheet pan, then pour the glaze slowly over the top, letting it drip naturally down the sides and into every eye socket and groove.