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Preheat oven to 350. Spray 10-inch (12 cup) Bundt pan with cooking spray.
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For cake, combine granulated sugar, shortening, peanut butter and brown sugar in large bowl. Beat with electric mixer at low speed until creamy. Add vanilla and then eggs, one at a time, beating well after each addition.
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Combine flour, baking powder, baking soda and salt in medium bowl. Add to peanut butter mixture alternately with buttermilk, beating after each addition until well blended.
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Spoon 2 cups batter into medium bowl. Stir in 3/4 cup sundae syrup.
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Spoon plain batter into prepared Bundt pan. Spoon chocolate batter over plain batter. Do not mix.
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Bake 1 hour 10 minutes to 1 hour 20 minutes or until toothpick inserted in center comes out clean. (Cake will rise, then fall during baking.) Do not overbake.
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Cool 45 minutes on wire rack before removing from pan. Place cake, fluted side up, on serving plate. Cool completely.
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For glaze, combine powdered sugar, 1/4 cup chocolate sundae syrup and vanilla in small bowl. Stir to blend. Add water, 1 drop at a time, until glaze is of desired consistency.
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Spoon over top of cake. Sprinkle with nuts.