Both starch and cellulose are polymers of glucose. However, the
individual glucose units are linked differently in the two. Humans
have an enzyme which is capable of breaking the linkages used to
form starch, but do not have one that can break the linkage used to
form cellulose. (If you want the technical terms, cellulose uses a
beta(1-4) link and starch uses both alpha(1-4) and alpha(1-6)
links.)