The basic colour concepts they refer to are синий="blue" and голубой="light blue".
The main colour is "синий". Most colours that are "голубой", may be considered a sub-shade of "синий".
СИНИЙ is a deep, earthly, material colour, the colour of the sea.
ГОЛУБОЙ is a light, airy colour. The colour of the sky (though, in poetic texts "в синем небе" is a set expression), the eye colour.
ГОЛУБОЙ also includes some shades between blue and green that would not be considered "синий". The word also has the meaning "a gay".