No. Distinct singular values do not force uniqueness in the spectral norm. For an explicit example take
The singular values of are . Every has matrix rank one, and its error in the spectral norm is
Thus there are infinitely many best rank-one approximations even with a strict gap between the singular values.
The same mechanism works for every under the question's positive singular values. Starting with , define
When the singular values are distinct, , so every has matrix rank , while
The spectral norm measures only the largest remaining singular value, leaving room to change retained components without increasing that maximum. This is the nonuniqueness of spectral-norm low-rank approximation. The exceptional case is unique for the elementary reason given above.

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