Let's start with the obvious: Why are your clothes on the floor? Buying a nice big hamper -- or several, if necessary -- for use where you usually change should solve the first part of the problem. If keeping your clothes policed alone doesn't work, it's time to figure why Rover's doing it and how to end the problem.
Pick up your clothes from the floor. This will accomplish two things. It will prevent Rover from pooping on them again. More important, it will tell you a bit about why he's doing it in the first place. If he goes out in search of something else you own, he might be trying to send you a message. Maybe he's upset with you because of recent changes in the household or your routine and behavior. He could be suffering from separation anxiety and going to the bathroom on your clothes because they smell like you. It doesn't sound like a demonstration of his love, but it might simply be stress making him do it.
Give Rover a pee pad. If removing the clothes from the ground doesn't solve the problem -- he's now pooping on the bathroom rug, for example -- you need to give him an alternative place to go. Most pee pads have a special smell that attracts dogs. If you put one in your shower or the utility room, he'll probably start pooping on that rather than your clothes. If he doesn't, he may have a behavioral issue that needs veterinary attention.
Walk him more often than you do now. A housebroken dog should be able to hold it until you're ready to go out with him for a bathroom break. If yours is not doing that, it could be that you need to walk him more often. He may be peeing on your clothes to hide the act. Young pups, energetic breeds and aging dogs might need three or more walks a day rather than two.
Take Rover to the vet if his peeing continues. He might be feeling sick and pooping on your clothes as a means of communication: He's innately trying to get you to recognize his condition. According to WebMD, a dog that starts urinating or defecating regularly in the house, having never done so before, might be suffering from intestinal parasites, inflammatory bowel disease or fecal incontinence.