Combine sugar, cocoa powder, arrowroot powder, espresso powder, cinnamon, chili powder, and salt in bowl. Whisk together egg and egg yolks in separate bowl. Stir egg mixture into cocoa mixture.

Scald milk in saucepan over medium heat until milk is steaming. Remove from heat. Whisk 1/2 cup hot milk into cocoa mixture. While whisking, pour cocoa mixture back into hot milk, and whisk until smooth. Return to medium heat, and continue whisking for 5 to 6 minutes, until pudding starts to bubble. Remove from heat and whisk in chocolate and vanilla until smooth. Transfer pudding to bowl, and cool to room temperature. Cover with plastic wrap pressed directly onto pudding; refrigerate until chilled.

To make Whipped Pumpkin Cream: Cook pumpkin and brown sugar with cinnamon in medium skillet over medium heat, stirring constantly, for 3 minutes. Transfer to bowl, and cool to room temperature.

Whip cream in stand mixer or with handheld beaters on medium-high, until soft peaks form, about 1 minute. Fold whipped cream into pumpkin until no streaks remain. Refrigerate until chilled. Serve pudding dolloped with pumpkin cream.