RGB to CMYK colorspace not available in Libre

Maybe you could try to do it another way: create a simple PDF (using any tool) with required CMYK colors; use ghostscript to convert it to RGB PDF; then check resulting colors in RGB and apply those to your LibreOffice text files? (Of course, it would only work if the conversion from CMYK to RGB and from RGB to CMYK is reversible in ghostscript)