It may not really be oil but corrosion floating out the top. I've seen it look and feel just like oil but it was just corrosion. But make sure you're not losing transmission fluid into the coolant.
The reasoning for not using Dexcool with the cap on the radiator is those system don't always do a good job of keeping the cooling system completely full which is need with Dexcool. It can be done though if the system doesn't have leaks with measures like a Stant 10230 radiator cap, Havoline Dexcool and keeping the radiator full and filling the overflow above the hot line.
Here's an old service bulletin:
Subject: Brown Colored Gel-Like Substance on Radiator Cap and Upper Filler Neck (Replace Radiator Cap and Clean Radiator Upper Filler Neck)
Models: 1997-2000 Buick Century
1996 Chevrolet Lumina APV
1996-2000 Chevrolet Lumina, Monte Carlo
1997-2000 Chevrolet Venture
2000 Chevrolet Impala
1996-97 Oldsmobile Cutlass Supreme
1996-2000 Oldsmobile Silhouette
1996-97 Pontiac Trans Sport
1996-2000 Pontiac Grand Prix
1998-2000 Pontiac Montana
with 3.1L or 3.4L Engine (VINs J, M, E, X -- RPOs LG8, L82, LA1, LQ1)
Condition:
Some customers may comment about a brown colored gel-like substance on the radiator cap and upper filler neck.
Correction:
Important
This condition is unique to the 3.1L and 3.4L engines and should not be confused with the condition described in Corporate Bulletin Number 99-06-02-012B -- Rust in Coolant System.
This condition is almost always confined to the radiator cap and upper filler neck, so it is not necessary to change the coolant. Keeping the cooling system full at all times should eliminate future recurrence. Replace the radiator cap and clean the radiator upper filler neck using the procedure and part numbers listed below.
Remove the radiator cap when the engine is cool.
Slowly rotate the cap counterclockwise to detent. Do not press down while rotating the pressure cap.
Wait until any residual pressure (indicated by a hissing sound) is relieved.
After all hissing stops, continue to rotate counterclockwise until the cap is removed.
Using a shop rag, clean the upper radiator filler neck of any residue.
Remove the coolant recovery reservoir if visually contaminated. Refer to the Coolant Recovery Reservoir Replacement procedure in the Engine Cooling sub-section of the appropriate Service Manual.
If necessary, clean the coolant recovery reservoir and all holes attached to it with soap and water. Rinse the reservoir and hoses with clean water and drain. Verify that the coolant can flow freely through the hoses.
Install the coolant recovery reservoir. Refer to the Coolant Recovery Reservoir Replacement procedure in the Engine Cooling sub-section of the appropriate Service Manual.
Refill the coolant recovery reservoir with a 50/50 mixture of DEX-COOL® and clean drinkable or distilled water to the HOT mark. Fill to the HOT mark to compensate for any air that may be in the cooling system.
Fill the radiator to the top of the filler neck.
Install the new radiator cap, P/N 10409635, making certain the arrows line up with the overflow tube.
Instruct the customer of the importance of maintaining the proper coolant level in the radiator and coolant recovery reservoir.
Parts Information:
Part Number Description
10409635 Cap, Radiator Filler
Parts are currently available from GMSPO
GM bulletins are intended for use by professional technicians, NOT a "do-it-yourselfer". They are written to inform these technicians of conditions that may occur on some vehicles, or to provide information that could assist in the proper service of a vehicle. Properly trained technicians have the equipment, tools, safety instructions, and know-how to do a job properly and safely. If a condition is described, DO NOT assume that the bulletin applies to your vehicle, or that your vehicle will have that condition. See your GM dealer for information on whether your vehicle may benefit from the information.