The golden garments are not worn by the Kohen when he enters the innermost chambers (I.E. The Kodesh Hakodashim, holy of holies)….. when wearing the white garments, he may enter the innermost chambers…..(Talmud, Yoma 32B)

בגדי זהב שאין כהן נכנס בהן לפני ולפנים . . בגדי לבן שנכנס בהן לפני ולפנים – יומא לב, ב

Throughout the day of Yom Kippur, the Kohen Gadol alternated between two different sets of clothing. Some parts of the day’s service were performed wearing his Golden Garments, called so for the gold and precious stones which adorned this set of clothing. These garments were made “for honor and for glory” (Shemos 28:2), from the nicest and most beautiful materials, as is befitting for all that is done in the service of G-d. The costliness and beauty of gold gave these garments impressiveness and grandeur, highly suitable for the most important day on the Kohen Gadol’s calendar.

Yet, for the parts of the service which required entry into the Kodesh Hakadashim, the Kohen Gadol would change out of these luxurious garments into the White Garments, a set of clothes made of solid white linen.

The Kohen Gadol’s two Yom Kippur getups teach two important lessons which we must incorporate in the service in our personal Beis Hamikdash, the temple for G-d which we have within ourselves. On the one hand, we must serve G-d with golden garments, with the best of our physical means. Someone who is blessed with material wealth cannot relegate his relationship with G-d to the spiritual realms of prayer and Torah study, but must quite literally invest his best and finest in mitzvos – first and foremost, in the mitzvah of charity.

In the innermost chambers of our souls, however, stands a Kodesh Hakadashim, a sanctum for a personal and conscious relationship with G-d. In this holy space, rich and poor are equal, and our charitable golden garments are not sufficient. In our Kodesh Hakadashim we must serve G-d wearing white; we must each pursue and develop a purely spiritual connection with G-d through Torah study and sincere prayer.

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—Likutei Sichos vol. 2, pp. 411-413