Glucose; starch is composed of two polymers actually, the linear amylose (alpha -1-4 linked Glc) and amylopectin (short chains of alpha 1-4 linked glucose with ramification at 1-6). As to how to determine the repeating units and structure, it was done in the 1970's using acidic and enzymic hydrolyses. And of course extensively confirmed since.
FINE-STRUCTURE OF VARIOUS AMYLOSE-PERCENTAGE CORN STARCHES - WAXY, NORMAL, AND AMYLOMAIZE By: MERCIER, C CEREAL SCIENCE TODAY Volume: 17 Issue: 9 Pages: 275-& Published: 1972