How is it "they're the same thing", but one has....
They both clean, but not the same product.
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This.
Near as I can tell from reading their respective MSDS:
Oxiclean
Sodium Carbonate - 55-65%
Sodium Percarbonate - 30-40%
Ethoxylated Alcohol - 2-4%
Sodium Carbonate is commonly known as washing soda, People add it to their laundry to make the detergent they use more effective by softening the water. Also, as an alkaline substance, it will break down fats and oils. Sodium Percarbonate is Sodium Carbonate with an extra Oxygen atom (Na2CO4 vs Na2CO3). When wet, it just breaks back down into Sodium Carbonate and Oxygen. The Oxygen creates bubbles and also provides something of a sanitizing effect. Ethoxylated Alcohol is a surfactant. A surfactant is essentially a detergent; it helps rinse stuff (dirt and grime) away.
PBW
Sodium Metasilicate - 30%
Phosphates and Surfactants (Unspecified) - 70%
Sodium Metasilicate serves pretty much the same function as Sodium Carbonate - it softens the water and makes it alkaline (though it's much stronger). Phosphates (think TSP) are alkaline cleaning agents. Surfactants, see comments above.
The two accomplish pretty much the same thing, but are in no way the same compounds.