Add the pineapple juice, Simple Syrup, rum, cream, coconut, vanilla and chile peppers to a blender, add ice to just above the liquid level and blend until smooth. Pour into a glass, garnish with a chile slice and serve.
Combine the sugar and 1 cup water in a small saucepan and bring to a boil. Cook, stirring, until the sugar dissolves. Remove from the heat and let cool completely. Keep covered in the refrigerator up to 1 month.