In a case like this, I shall say it's not a hard thing to spot cause it's pretty simple to spot fake leather, pleather and fake suede.
When you're out shopping for a pair of shoes or boots, you will automatically know just by the material itself. How it feels, smells and of course, if it is all weather proof because if your shoes aren't waterproof, you will see how fast the material eats away from just a simple rain drop that gets on it or any liquid of any kind as fake leather also known as pleather will never hold up in bad weather.
More like the new car smell, leather always has that great smell that I'm addicted to all because of the smell alone. Which is how you can definitely tell if your footwear is leather and not pleather.