Standoffs have nothing whatsoever to do with whether or not you release ESD to the case. They also don't protect anything from ESD. They all they do is isolate the backside circuits and solder points from touching ground. If you look at the area where the standoffs are, you will see that they are completely isolated. They are not there to provide ground, in fact, many motherboards or prebuilt systems use plastic push pins as standoffs. All the ground your system needs to the motherboard is provided through the cabling.
The discharge you experienced may not be a "biggie" and you probably didn't harm anything, but you may have. ESD can cause micro-damage that begins to send sensitive components on their way to an early grave, most especially if it's a recurrent problem. I wouldn't want to see it happening regularly and I'd take steps to see that it doesn't. In most cases, the discharge will likely be dissipated through the case's ground, but sometimes it can have an effect on hardware, especially if, like you saw, there are clear indicators that the system was affected by it.