Colors in Spanish usually work as nouns, besides being adjectives. Color nouns are always masculine: el blanco, el negro, el azul, el rojo; even color nouns derived from feminine nouns are masculine: el naranja, el violeta. This is probably because the noun forms are understood as referring implicitly to the word color, which is masculine (el naranja = el color naranja, etc.).
In the English phrase "Orange is the New Black", the subject is "Orange" and both "Orange" and "Black" are nouns, so if we were to translate it literally, it would be El naranja es el nuevo negro. As far as I know this is not done (the title for the Spanish edition of the series is left as in English), which is just as well because the literal translation sounds awful.
You can use the color nouns with the definite article as above, for example, to speak of el azul del mar ("the sea's blue"), or with the indefinite article, for example un verde tan oscuro que parece negro ("a green so dark it looks like black"). This is no different from English, by the way.