In terms of transportation across the country, I think FedEx is marginally better than UPS. That just gets the package to your vicinity. On the other hand, we've had varying experiences with the local drivers of both companies and the final safe transportation to your door does rely on them. FedEx has been better here, but last time I spoke with Mica, they've had better luck with UPS in their area.
Ten years ago when I was doing a lot of international work, DHL was the most reliable for safe international delivery. Don't know what things are like now.