Professional sounding is in the ear of the beholder, and to some degree dependent on the person using the library. I've heard absolute hack jobs that used the most respected libraries, and I've heard mockups that used only Garritan Personal Orchestra that sounded great.
That said, I think GPO is limiting. It is a great place to start because of those limitations, and if this is your first virtual orchestra purchase you should consider it.
Kirk Hunter's libraries are a major step up, but the sound of his samples is not for everyone. It is very close, almost aggressive. I still use his Concert Strings 2 and Concert Brass 2 libraries - they cover a very wide range of section sizes, and most of the articulations you'd want. I have not yet checked out CS3, but I will. I also use the winds from his Diamond collection, and his SpotLight Strings. Be forewarned, his libraries require a great deal of work at mix time to make them sound their best.
If you are looking for something more "out of the box" I'd suggest listening to demos from Cinesamples, 8Dio, Spitfire, Project Sam, SoundIron, Audiobro, Orchestral Tools, and others. They all sound different, they all approach articulation control differently, but they all sound wonderful!
My current template uses the Agitato and Adagietto strings from 8dio, and the core winds and brass from Cinesamples. I also make heavy use of Orchestral Essentials from Project Sam.
Which brings up an interesting division - sample libraries can be instrument based or ensemble based, with shades in between! Orchestral Essentials is similar to the Albion range from Spitfire - it is recordings of entire ensembles in situ. Can't beat if for the sound, but it makes arranging a little more challenging. The Adagietto strings were sampled by section, no soloists (you have to spring for Adagio to get that<G>!). But at least you have Violin, Viola, Cello and Bass as separate sections. The Orchestral Essentials Sustained Strings, in contrast, is the entire strings section mapped across the keyboard.
The other thing to consider is whether or not true legato is important. A lot of work goes into sampling the transitions, and it drives the cost way up. It also requires a great deal more care in sequencing.
I am not a big fan of the NI phrase based libraries (such as Emotive Strings and Action Strings) - nothing specifically wrong with them, I just don't find it easy to work with them. I do have the original Session Horns and Session Strings libraries, and they can be really useful in some settings.
Lastly, budget. Good libraries are not inexpensive. You probably need to be prepared to spend several hundred dollars or more to build up a good orchestra if you don't start with something like GPO.
That's the five cent tour, post back if it created more questions than it answered.