Hi Anarel,
Are the chapter headings in your RTF marked as headings? For instance, if you loaded the RTF into MSWord, the chapter headings need to be given one of the in-built Heading styles, i.e. "Heading 1" or "Heading 2" etc. not "Normal", "Normal (Web)" or "Body Text".
If you have converted from PDF to RTF using one of the many free "PDF to Word" utilities around, there is a possibility that every paragraph is "Normal", i.e. Calibre may not see any difference between the chapter headings and the body text.
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