One word of advise. If you store items in the workbench, the system can break them down for the basic materials, steel or wood for instance from guns.
So, what I would do, is to build some wardrobes or a metal chest to store your gear in, until you know what you want to use.
As for crafting, go to the armor or weapons workbench and see what kind of options are available to you. Every mod also shows you how the weapon will change.
Receivers increase damage, help with weapon recoil, but some can also lower the range of the weapon
Scopes will increase the range of a weapon
Stock will also help with recoil and accuracy
Magazines can increase ammo count, but also decrease reload speed
There are a few other options, like increasing rate of fire for instance.
A lot of the mods will also increase the weight of the weapon
Also, you will only have access to a few basic mods, until you raise your Gun Nut perk.
You also need the various components, in order to create mods. Most of them require screws and oil, so make sure to store all your junk in the workbench. The system then will use the components of the various items stored there on any crafting station.
When you craft a mod, it is automatically added onto that weapon and the standard one will be in your inventory. You can store mods in the workbench as well and if you find a gun with a better mod, just apply the standard one to that gun and then you can apply that new mod to your other weapon. Mods are weapon type specific though. Any 10mm mod, should work with all 10mm pistols, while a Pipe Rifle mod will not work on a Combat Rifle (at least that's how I understand it).
Same goes for armor. In order to modify say the leather armor, you will need leather, which you can harvest from various animals (hides), as well as other components.
In order to create better armor, you also need to level up the Armorer perk.
I got both Gun Nut and Armorer at lvl 2 at the moment and was able to create some powerful guns. I have a Scoped Powerful Combat Shotgun that does 75 damage (I'm lvl 15). And I'm using Shadowed (helps with sneak) Leather Armor pieces, some with pockets (increase carry weight, and my chest piece is lined with asbestos, so I won't take fire damage).
The Chemistry Crafting station also uses components stored in your main workbench. You can also use it to combine some basic chems you find and make some powerful ones with it.
Like Buffout and Jet (Buffjet), which slows time, raises your strength and endurance and I think HP or something like that.
I collected a lot of guns at the beginning, but stored them to sell when I finally found a merchant. I actually kept modding my 10mm pistol at first and I still use that, in addition to my shotgun and sniper rifle.
I think the pipe guns are rather weak, but the .38 ammo is plentiful. Maybe they will be better at a higher Gun Nut level, but I rather collect "real" guns, instead of home made ones (like the Combat Shotgun or an actual Sniper Rifle). I did create a powerful pipe gun sniper rifle, but the rate of fire was much too slow.
Just play around with the various options and see what you come up with.
A lot of perks are also related to increasing damage from the various weapons. So, you should decide whether you want to go with automatic weapons or not, since there are 2 different perks for regular weapons and auto weapons (under Agility).