For harder materials worn around just the shaft, put them on while soft and adjust as needed.
When worn around the whole package, getting it on is a bit involved and somewhat tricky. For this you need to be soft and your ball sack needs to be in a relaxed state. This means that it needs to be warm for your boys; I find the easiest way to do this is to take a hot bath. This gives the scrotum more stretch and it will make it much easier to work with.
Now for this you will need to apply lube all over the shaft and package, the more the better. Start by sliding one ball through the ring and the slide the second one through. Follow this with folding the penis and shoving it through. See why you need to be soft? I find this can be hard at times, especially when I know a night of fun is coming. As soon as the lube gets spread around, my penis starts to grow which makes things more difficult. This will take some practice but it does gets easier the more you do it.
Note: As long as you are not hard, these kinds of rings can be worn for longer periods. In fact, some guys may like to wear them for extended periods. It will make your package look bigger and the weight can be stimulating in its own way. This might be the key to putting them on until you get the hang of it.
To remove, just wait until you go soft and reverse the process. Although, when soft it is possible to remove the balls first then just slide the ring off the penis.
As you can see, harder materials take more effort to put on and off. This is why it is important to be sure about size first before wearing them. They do not come off fast. I might add that it is better to get something a size larger, while it may not provide as much restriction; you could wear it for longer periods of time with little worry.