Reporting back with my experience. I have to agree with those that said not to waste the $25 but take my chances on standby.
I did use the FlyNow feature for my outgoing evening flights (CHS to DTW to LGA) and was given the option of 2 earlier flights into EWR. I chose one of those, paid my $25 and took the earlier flight out. Once I got to DTW though my connection into EWR was cancelled due to MX issues so I was rebooked on a flight into LGA that arrived a mere 2 hours before my original flight. Not worth $25 for that although I do know that MX delays can't be helped.
On my flights home (LGA to DTW to CHS) I called NWA at 2am before my 6am flights and was told that I could go online at 3am and see which flights were available for FlyNow or I could just try to go standby for no fee. The NWA agent on the phone advised me that EWR was really my only option since the later flights out of LGA and JFK were oversold. I checked online at 3am and again at 315am and there were NO choices for FlyNow. My only options at that point were to pay the $100 fee for a confirmed seat, go wait for a standby seat or take my original 6am flights.
I arrived at EWR at 2pm to be put on the standby list for the 6pm departure and the confusion began. I was automatically SSSSed since I changed departure airports (even though it was still a NYC one) which actually didn't bother me since that line was shorter than the regular TSA line.
I am not a fan of standby - especially on the last flights of the nite. My last leg home had ONE empty seat so I just barely made it onto that plane.
FlyNow is so hard to use since there are no defined rules and no one on the phone can help you with the program. I honestly got a different answer to the same questions from each NWA agent that I spoke with. Finally I got a phone agent named Jim on the line on Sunday who was a wealth of info (why can't they ALL be like Jim!!). The fact that you have to be able to go online to use the function is a pain if you are literally on the road.
FlyNow - Buyer Beware. I'll stick with Delta and my Same Day Confirmed that is free with my GM status.