Shawn, in my opinion, the best time of day to work with the bees is when the bees are flying. Meaning, you do not want to work with the bees when they are all home. Figure out the time of day when it is warm enough that the forage bees are headed out the door. Give them some good time to mostly have left the hive. They will of course be returning and leaving all day, but don't go in too early, when they are all home. The less bees to deal with, the easier it is for you.
When the weather is sunny here, I don't go into the hives until about 9:00 A.M. at the earliest. It wil differ greatly from area to area. Of course, if you can avoid it, don't go in there when it is windy, rainy (that is a given), or on coool, cloudy, dark days. You will find many more bees home during these types of periods. If it is really necessary to go in the colonies on the more adverse weather days, remember to suit up, protect yourself. I never work the hives anytime without a veil. If you use the veil, you will always feel the most important parts of your body are protected. That being your head. Learn to work the hives gloveless, unless you have really aggressive hives (then you should think about requeening, an aggressive hive is not one that any beekeeper should allow, my two cents here).
When you work with gloves, you run the chance of easily squishing or harming one of the girls. THis causes the alarm phermone to be released, and you can bet your two dollars the hive will become defensive. If you work without gloves, you can feel even if you are coming close to a bee, and avoid touching or harming them. I have not used gloves in the over two years of beekeeping now and have yet to be stung on the hand. The only time that I have been stung on the hand is when I touched a bee inadvertently, and yep, received a sting.
When I get a sting (which is very very rare), I always smoke that sting area immediately. This disguises the scent of the sting pheromone and further attacks to that spot are diminished. This is how I work with my hives. You will received varied comments from members, listen to them all, learn, chose your own tactics. Every beekeeper has different opinions. Have a wonderful day, best of this beautiful life, great health to all. Cindi