Oracle iProcurement REALM is nothing but a definition of Rules. You can group Item categories under a REALM and attach the REALM at user or responsibility level using Securing attribute ICX_POR_REALM_ID.
Information on the implementation guide is enough to understand this feature.
Below are the ones that are not mentioned in the document.
1. REALM are effective only for Catalog items, Non catalog items will not get restricted by the REALM.
2. You need to bring the Item categories to define it in REALM screen through
E-Catalot Admin --> Loader Values. This submits a concurrent program which will load the Item categories which can be used in the REALM screen.