Then you'll need to eliminate starch first, and this may be quite time consuming and / or generate artefacts. And do not forget that a large part of these non-starch polysacharide is not soluble (VERY not soluble, this is in particular a distinguising feature of cellulose) so you do not extract polysaccharides, you extract the rest while keeping non starch polysaccharides insoluble.
you can try a dietary fiber procedure (the ymor eor less all go gelatinize starch, digest starch enzymatically, sometimes digest proteins enzymatically, precipitate the remaining polymers with ethanol, you'll end up with a material normally composed primarily of polysaccharides, plus proteins, lignin and some minerals, quantify and substract proteins and ash. And to quantify the polysaccharides you can just weight, if you want to do a Dubois / phenol sulfuric assay you'll need to dissolve them first in concentrated sulfuric acid (Saeman procedure).
Hi, prepare a fine flour from the samples, hydrolyze the starch fraction using alpha-amylase + glucoamylase (you can use Megazyme kits fo DF or RS), recover the rest with centrifugation. by the way, there might t be 2 problems, 1- presence of lignin 2- presence of resistant starch in your sample.