Address any insect problem that you have in your barn. Some insecticides are ineffective on spiders themselves because they are designed to work primarily on insects (spiders are arthropods). However, those spiders that are not affected directly by the insecticide tend to relocate after you cut off their food supply.
Destroy and clean away any webbing in your barn when you find it. Keeping any area clean discourages a spider population, but consistent web removal ensures that you rid your barn of any egg sacs that could fuel another outbreak. It also forces spiders to make contact with treated areas that they are able to avoid when on the web.
Kill any residual spiders with a pesticide that is specially created to handle spiders, rather than an insecticide. Read labels carefully to select one that will not be toxic to anything inside your barn, such as livestock. If you choose to go "green" with a natural alternative, spiders show an aversion to lemon-oil products. Chestnuts also make spiders vacate the premises.