As noted above, seams tend to be the problem. Tent fly seams, the usual beneficiary of said silicone goop, are practically always flat seams. Luggage seams rarely are, and that makes them much harder to apply such a treatment effectively (which, in turn, is why practically nobody bothers).
The point of a silicone spray on the outer would be much like the beading coat on waterproofs. to stop water wetting out the face fabric. And that's a useful thing in itself because you end up carrying less water around with you, but isn't the same thing as waterproofing. Once enough has soaked in the surface tension keeping water out will be broken and, silicone spray or not, it'll leak.
For some values of "best"...
I think it's good (my Brompton bag is a Carradice cotton duck number), but "best" normally boils down to context. Cotton duck is pretty heavy stuff and harder to clean than coated synthetics, for example.
I've been using Orts for over 20 years and I've never had an obvious problem with internal condensation, and in fact this is the first time I can recall anyone raising it as an issue. You can get condensation on pretty much any surface if the air around it is moist enough and the temperature falls to its dew point, but I really don't see that as a problem in panniers.
Price?
Carradice Super-C 5 litre handlebar bag is £89.95 at their web site, Ortlieb Ultimate 5 litre bar bag is £72 at theirs.
Carradice Super-C 28 litre universal panniers, £109.95, Ortlieb Sport Packer 30 litre, £145
Carradice Super-C 54 litre rear panniers, £149.95, Ortlieb 40 litre Back Roller (widely available at 140), £150 (widely avaialble at ~ 130)
So bar bags a bit less, per volume panniers a bit more, but not stupidly more than Carradice.
And I prefer Orts over Carradice for panniers mainly because I think the fittings are better more than anything particularly about the material. Carradice are likely better for those who like separate pockets built in, and so on, but for something that's going to last well over a decade in regular use the price on either is reasonable.
Pete.