Try taking them to a shoe repair specialist, they also do cleaning and can tell you the best products to use to get the stain out (or do it for you, paying them to do it is usually cheaper than buying the cleaning products) Without knowing the exact material of the shoes (suede, leather, patent, imitation suede, lace, satin) and exactly what the stain is from the general public won't be able to advise, but a shoe repair specialist will be able to tell you the answer after just looking at the shoes.
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