As I type this I’m listening to Schubert’s Symphony No. 9 “The Great” the 2nd movement (Andante con moto) now I’m by no means consider myself very knowledgeable, but even on my PC the hairs on the back of my neck are moving. This is from a cheep Naxos version [8.550502]
Sibelius – Finlandia personal favourite is the EMI, Halle Orchestra, under Sir John Barbirolli [CDM 7 69205 2]
Mozart – Symphony No. 40 [Telarc CD-80139]
Mahler – Symphony No. 1 [Telarc CD-80066]
Delibes – Coppelia [Capriccio 10 073]
Bizet – L’Arlesienne [Naxos 8.550061 & includes Carmen]
Are all what I would consider accessible, but you don’t have to go down the classical route fully, Elmer Bernstein’s - The Magnificent Seven, is well, magnificent. Check out some of the other movie works, Star Wars, Superman and so on.

Telarc do a compilation I believe [CD-80141?].
As for piano if you can get a copy, on vinyl I like David Sancious – The Bridge, for CD, Micheal O’Suilleabhain – The Dolphin’s Way[Venture CDVE1] (the last two are not Classical as such, just classic's) and Darryl Way (with Opus 20) – the Human Condition [Venture CDVE8]. But you could resort to the Previn/Royal Philharmonic version of Tchaikovsky’s Piano Concerto No. 1 [Telarc CD-80124]. But I find Jazz allows more insight into the Piano, but perhaps that’ll be another thread?
Paul
Just edited in the Disc numbers, don't really know if these are that good, but Telarc has always been a good bet. I believe Penguin publish a Classics guide or you could try the monthly 'Gramaphone' (is this still going?) or Hi-Fi News of course for some pointers.
and I forgot, Holst - Jupiter (from the PLanets, the best bit) LSO/Hickox [IMP PCD 890]