If you want some solo, exposed instruments on top of the ensembles, check out the SWAM instruments from Audio Modeling. They also have a new String Ensembles product, though I haven’t yet tried it.
Virtual orchestral productions are almost always offline efforts. To get expressive results with samples, we often need to keyswitch to different articulations, select samples with different vibrato, and shape the sound with the mod wheel. If you have an effect, like a stab or a fall, don’t overuse it, or you can hear the sample repeat. On the other hand, if you use synthesis, you can perform every note uniquely, and get dynamic vibrato and attacks, rather than whatever is baked in.
To really get it to sing, use a breath controller.
A sample library is better for people who input notes with a mouse. Synthesis is best for performers. When I was doing a lot of sound for pictures, I only had sample libraries and used both techniques.
For live, I like playing SWAM instruments with the breath controller. Doing that with a solo instrument over a prerecorded backing track of the ensembles could be good, practical approach for The Wall. (I saw it live in LA. The orchestral parts were all prerecorded.)
Another trick is to use scripting to create auto harmonies or dynamic keyboard splits. Shaping all the voices of a harmony with one breath controller isn’t ideal, but it’s still effective.
Anyway, SWAM instruments can be a good investment for those times when you need a sax, trumpet, clarinet, or violin line and lack a live player. The mod wheel works, but a breath controller frees up the left hand and can be better showmanship.