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Long term, the 96 will be the better investment (IMO), plus I think it would be the better buy now, all things being equal. I guess it depends on how you plan to drive it.
If you're going to show them you'll have a better chance at placing with the 96. Many more C-5's in the shows to compete against. But I agree that you should drive both and then choose. They are definitely two different animals.
Neither is rare, and the CE has too many miles to be collectible anyway. Drive both and pick which you like best.
Despite what many C4 lovers may claim, the C5 is indeed faster, BUT that doesn't mean you should buy it.
In the C4/C5 world there are only 2 cars in my mind that are truly (for the long term) collectable - the C4 ZR-1 and the C5 Z06. Both have a place in Corvette history. The ZR-1 is probably the better investment bet given the limited production numbers, the visual look of the engine, and the fact that it is the first true post muscle car age performance Corvette. The C5 Z06 is a great car but it seems to me that it will be overshadowed by the C6 Z06 (never mind the new ZR1).
You would love the 2001. I drive one daily and love it.
The LT4 is special as its a one year motor. It would be the car to have down the road over the 2001 but we are talking a loooongg way down the road like 2026.
As others have stated, there is not much if any investment value on a CE or a 2001 C5. The C5 is a better car all the way around. I would go C5 and never look back.
Neither of them will likely be a great investment. Try them both and buy the one you like best - they will have quite different manners.
Neither of them will benefit your pocket. They are both cars meant to be driven not stored in my opinion. Test Drive them both and get a feel for what you like better. However if you need a reason to tell your wife you need another corvette, just grab the CE and say its an investment to cover yourself.