Yes spilled engine oil can catch fire especially if the engine oil got spilled on the exhaust manifold which gets very hot.
When you start your vehicle up and there's spilled oil on the exhaust manifold you'll likely soon see some smoke coming from under your hood.
If it's just a tiny bit then the engine oil will usually just burn off without catching on fire but if you spill too much engine oil onto the exhaust or other hot engine components then it could lead to a vehicle fire while driving down the road.
So remove any spilled engine oil from the exhaust before taking off in your vehicle and be careful to avoid spilling any engine oil.
The engine oil is combustible and can easily catch fire.