For pure demo / "show off" vocals, the following are hard to beat. (Not all not contain great, timeless material, but they DO sound good.)
1. Thelma Houston & Pressure Cooker; LP: "I've Got The Music in Me" -- Sheffield Labs
2. Amanda McBroom; LP's: "Growing Up In Hollywood Town", or "Dreaming" (released on both Sheffield Labs and Gecko labels)
3. Opera; CD: "Arias for Farinelli", by Vivica Genaux. One of the most phenomenal female voice recordings I've ever heard, with superb instrumental backing by a period instrument baroque orchestra. Chosen as one of Gramophone Magazine's "Top 10 Recordings of the Year" for 2004.
4. Joan Baez: LP's: "Diamonds & Rust", or her early Vanguard recordings that have been re-mastered and re-released in audiophile editions.
5. Willie Nelson: Half-speed mastered LP copy of "Stardust" -- no, I have not lost my mind. Everyone knows the sound of Willie's voice, so this recording makes an excellent "litmus test". It is VERY well recorded and also has some great music.
6. Mark Murphy: in my personal opinion, one of the all-time great male jazz singers. The late Joe Williams was also one of my favorites, but Murphy is superbly hip and almost always has great jazz musicians providing backing on his recordings. Murphy has a number of good recordings, but my personal favorite is "Bop For Kerouac".