LATIN DICTIONARYLexicon Latīnum
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“chief” in Latin

The English word chief itself goes back to Latin caput, through capus.

Riddle & Arnold A Copious and Critical English–Latin Lexicon, 1864

chief s.
caput; princeps; *reipublicae gerendae princeps: to make anybody the chief of a confederacy, *foederis principatum deferre alicui: the chief (in rank and dignity) of a state, vir primarius populi: dux (general term): auctor: princeps (he who takes the lead in anything).
Commander in chief, dux belli: imperator: praetor (leader in war, the latter especially of Greek commanders in chief στρατηγός).
Leader, caput: signifer: fax (chief of a party, a conspiracy, etc): the chief in a civil war (who gave the signal for its breaking out), tuba belli civilis (Cic. ad Div., 6, 12, 3): the chief of the cavalry, magister equitum; praefectus, with or without, equitum (general term).
chief adj.
primus (first in order or time, with others after him): summus: maximus: praecipuus (post-Augustan, principalis: except in causae principales: opposed to secondary causes): primarius (first in rank, dignity, or value). The chief men in the state, capita rerum or reipublicae: primores: primores civitatis or populi (by connections, birth, power, credit), principes (by intellect, talents, powers of debate, activity, etc.; hence distinguished above primores, who are a body): proceres (the chief by natural position, nobility opposed to commonally): optimates (as a political class, the aristocracy). The chief point, caput alicujus rei: summa alicujus rei: cardo alicujus rei (on which all turns, Varr. and Quint.): momentum (ῥοπή, the critical, decisive point). The chief good, summum bonum. It was always his chief care, ei semper maxima or antiquissima cura fuit: to make anything one’s chief business, omne studium in aliqua re ponere. This is the chief point, hoc caput est: hoc maximum or primum est.

Quick answer

What is the Latin word for chief?
The usual Latin words for “chief” are caput, prī̆nceps, signifer; also fax, dux, auctor. The right choice depends on the sense; see the distinctions below.

Entry from J. E. Riddle & T. K. Arnold, A Copious and Critical English–Latin Lexicon (rev. C. Anthon, New York: Harper, 1864), digitised by Fergus J. P. Walsh, CC BY-SA 4.0; Latin markup adapted by latindictionary.co.