You can't kind of calibrate LibreCAD to the image, you have to adjust the image to LibreCAD.
There isn't really much more to explain about the procedure. By default an image is imported with one unit per pixel. A bitmap-image doesn't really have a physical size, some carry an optional dpi-value with them. When importing the image you can set a scaling factor in advance (what is a bit useless as you only can measure and calculate after having imported), or if the image is a scanned one with a known dpi-value, set that ( can also be tricky depending on your drawing units).
When taking the measurement from the graph paper better take the largest possible distance for more accuracy, let's say 20cm. But be aware that scanners and optical lenses produce distortions, so there always will be some inaccuracy.
Now divide the distance to be ( the wanted one) by the measured distance and scale the image with that factor.
Now an important issue I have forgotten to mention is that after scaling the scaled image seems disappeared. You have to perform an "Auto-Zoom" to bring it back. This is a bug that urgently should be repaired.
Good luck and please report back if this solves the issue.