Opportunity is missed by most people because it is dressed in overalls and looks like work. - Thomas Edison
There are many ways to do this in photoshop, here is one easy way showing in the attached image, some other methods would be to use the gradient-map adjustment, or go to multichannel from greyscale or just duplicate a neutral greyscale rgb red, green, or blue channel and change to a spot-color and set to the color you want... set a substrate channel and set the color to have it going over a shirt color you could change. Do you have the image you are working with and want to see some options, using built-in aspects of photoshop?