Cosmetic compositions, systems and methods for conferring responsive durable shaping of keratinous fibers employ at least one shape memory polymer that includes a three-armed branched polyethylene glycol (PEG) based polymer that is functionalized with one or more metal-coordination active groups. The shape memory polymer forms a crosslinked network coating on a substrate, for example a substrate selected from keratinous substrates, for example, hair. Hair coated with the shape memory polymer and treated with an oxidizing agent can be shaped, locked into shape, and reprogrammed by modulation of pH. The coated hair retains durable shaping properties through at least one shampoo treatment. The cosmetic compositions, systems and methods provide durable and reprogrammable durable shaping of the keratinous substrate, for example for styling hair.