Preheat the oven to 375 degrees. Place the potatoes in a large pot; add enough cold water to cover by 1 inch. Bring to a boil, reduce the heat to medium-high and cook until tender, 30 to 40 minutes; drain. Peel the potatoes while still warm, then cut into 1/4-inch-thick slices.
Using a sharp knife, cut the peel and pith from the oranges; cut into 1/4-inch-thick slices. Coat a 9-by-13-inch baking dish with cooking spray. Alternate the potato and orange slices in the dish, overlapping slightly in crosswise rows.
In a medium saucepan, melt the butter over medium heat. Add the brown sugar and pecans. Cook, stirring constantly, until the sugar melts and a smooth sauce forms, 2 to 3 minutes; spoon over the potatoes and oranges.
In a small saucepan, bring the orange juice, maple syrup, cornstarch and cloves to a simmer over medium-high, whisking often, until thickened, about 5 minutes. Pour over the potato and orange mixture. Bake until the juices bubble and thicken, about 15 minutes.