LibreCAD can't use ttf fonts and is limited to sticky or outline fonts, so no filled letters possible. You have to live with what is offered.
The font for dimensions is set at Options - Current Drawing Preferences - Dimensions - Text Style.
The dimensions settings apply to all dimensions in a drawing, can't be set individually.
Edit: you have to live with what is offered - not quite true. There is a tool to make your own outline font from a ttf - ttf2lff:
https://dokuwiki.librecad.org/doku.php/community:fonts