So I guess two things here. First and foremost, is the obvious. Does "/mnt/yourvolume/..." actually exist on your FreeNAS box, or is that just copied out of a walkthrough?
Second, NFSv4 has a different way of allowing access to shares than NFSv3 does. NFSv3, you specify on FreeNAS what the connecting box's access looks like (most often I've seen people use Maproot User = root, and Maproot Group = wheel which isn't the best of things to do, but I guess it works).
NFSv4, as I understand it, actually lets you set username/password authentication, which Proxmox's GUI may not be setup for. I'd say uncheck Enable NFSv4, set Maproot User = root and Maproot Group = wheel, and test it. From there, adjust your user and group to fit the security you like.
Also please note that when you remove an NFS share from Proxmox, it does not automatically unmount the NFS share. It just removes it from the GUI. You either have to reboot, or login and umount the NFS share before you can add an NFS share with the same ID. This is a situation that only comes up in NFS troubleshooting and fine-tuning.
No, Proxmox is super awesome about creating a standard layout when it is presented with storage. So whether you give it an NFS share, or a second disk or whatever, it will create I think it's 3 major directories: dump, images, and template. When you upload your first ISO to Proxmox, it will automatically create an ISO directory under Template.
So in short, just give Proxmox the storage, and tell it what you want to store there.
Yes, in this case, on your NFS share in FreeNAS, disable NFSv4, and set Maproot User to root, and Maproot Group to wheel. This basically tells it to treat every connection to that NFS share as if it were root. Red Team will love you for it. But it's a valid way to get it working and learn about it, as long as you know you should experiment with it later on to figure out how to secure it better.
So here in the Proxmox storage menu, use that drop down menu next to Content to tell it you want to store ISO Images (and whatever else you may want) on that NFS share, and then Proxmox will handle creating a directory structure for all of the items you selected.
Alternately, if you'd rather manually separate them yourself, there's nothing stopping you from creating a share for disk images, a share for ISOs, and a share for VZDump Backups. But I don't know that you really get any benefit from doing this, and it's a lot of extra work.
Edit: Also when looking at your backup storage, don't forget that you need enough space for n+1 backups. Meaning if you set the max backups of your backup storage device to 5 backups, it needs to be able to hold 6 backups, as Proxmox will not delete an existing backup until it has a backup to replace it with. It's one of those things that makes perfect sense when you say it out loud, but I've still seen people get burned by it.
When I set a dataset to nobody and nogroup, anyone who isn't nobody or in nogroup has no access to it. I've never seen it function like guest access before.