Let us see if I got what you're asking for right... You want it so that certain spells hit very often and so that when carrying certain weapons you also hit ofter?
If this is what you're asking for than the anwser is quite easy
In the RMXP database under Skills their is a "stat" called "Hit". All you have to do is adjust this to a higher number on the skills you want to have hit often.. Now hit is not affected by enemy evade rate, and so on. All spells have 100 hit rate in the standard database but seeing as they dont always hit all you have to do to insure 100% hit chance is change the hit to a much higer value, but thats easier said than done... as the max value for hit is 100%... so for spells im going to admit i can't help you (one option being ofc reducing enemy evade chances, but this make all spells and attack more likely to hit.) with the weapon however i can help.
Go to states than make a state called Hit( or whatever you want) make it so that the hit rate % is 200 or any value you want over 100, as that will make it faster (not sure if 200% will make it so that all ur attacks hit but it will certainly help alot also 200% is the max
Now go to weapons choose the rod for example and go to state change and click on the hit or whateer you named it. Now this will be shown when in combat underneath your character picture, to avoid this simply change the rating (we are under states again) to 0 then it will never be displayed
also as this hit rating increase will remain even after you take off your weapon, you will need to put a state change "- hit" on all weapons you don't want to have an increased hit chance with
hope i helped. This was all i could think of atm its 06:49 and i can't go back to sleep
if i figure some better solution out ill notify you, but for now this is all i can think of
And sorry but the state change WILL also affect your spell casting and as far as im aware it's not possible to do what you want without a bit of scripting
Also for user standard attacks you will need to do some scripting as that isn't shown in the database, if i'm not mistaken.