Go to the OpenOffice website (or LibreOffice if you've actually got that one) and there's a documentation section where you can download free manuals. The Writer manual is a 500 page illustrated pdf book! The chapters cover program basics, editing, formating, printing and exporting, styles, graphics, tables, templates, mail-merge, contents and index, master documents, fields, and maths.
Templates are really useful and worth learning about, if you often want to produce a document with a standard set of page, paragraph, or heading types.
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