Basically:
#info
is used to discover information about a XMPP entity.#item
is used to discover items associated with a XMPP entity.
#info
query results will show you amongst others the supported features of a XMPP entity (e.g. XHTML-IM support).
#item
query results will show the available items of a XMPP entity. For example the XEP-0045 MUC component of a XMPP service. But any other available service/component could show up here.
One could also say that #info
is used to query the features of this particular entity, while #items
is used to query for "sub-components" of that entity, which itself are usually be queried with #info
for their features.