1. the BLACK and BLUE tiles are normally for water. each black and blue section is separated into 3 x 4 sections. how they work is that each column of a section (starting from the left) is one frame of animation; i.e. if you compare it to the basis chipset, go left to right in one of the water sections and its like 3 frames of animation. you get 3 frames of animation per 3 x 4 section. all the different water tiles are there so that they can autotile, i.e. have it so you can just 'draw' water on your map... they cover all the angles you have to have to make your water look smooth. if you copy the structure of how they did it (i.e. horizontal water, then vertical, etc) from a chipset with water you should be fine. common uses are: water, deep water, and water with snow around it.
2. the GREEN and YELLOW section right under the water is for animations. you can make 3 tiles that animate, with 4 frames each. each column is one tile; the animation starts from the top. if you compare it to the basis chipset from the RTP its got a waterfall, a whirlpool, and an ice-block like thing... all the animations start at the top and end at the bottom, frames each. you can put things like animated flowers, waterfalls, or just random animated extras here.
3. the LIGHT BLUE and BLACK and GREY and BLACK sections are all for autotiles; there are no differences between the two colors as far as I know of. how the autotile sections work is this way: the top left tile is if you just drew a single tile in RPG Maker, the top middle tile is what surrounds it, and the top right is for bridging corners. the bottom 3x3 section of it (stay alert, haha, the whole section is still 3 x 4, nothing different) is if you drew a 3x3 'square' of the tile on RPG Maker. RPG Maker will take all the tiles and information from each of these sections so you can draw smooth tiles. you get 12 auto tile spaces not counting water. you can put things like grass, dirt, snow, house borders, etc. here.
4. the GREEN and YELLOW section is where you place any tile thats not an autotile or water, and also has NO transparency. things can be put in any order here and it doesnt matter. use this area to just put any extras you have in, such as mountain structures, stairs, variants of floor tiles, anything you can think of that DOESNT have transparency. but on the blank chipset image, the one tile where it says TRANSP. MUST be kept open; it can be any color you like but it has to be a different color than anything on the tileset. thats your transparent color. when you place that on the map, it takes the tile away and shows a parallax background that you can choose for any map; thats what its for.
SECOND LAYER
5. anything ORANGE AND BLUE is designated for the second layer of tiles. this is where you put things that have transparent parts, i.e. tree tiles, flowers, chairs, rocks, statues, etc. the color surrounding it is the transparent color: the color that WONT show up in the editor/ingame. it should be the same color as the transparent tile in the GREEN and YELLOW section we just covered up above. tiles in here can be in any order and it doesnt matter where they are placed. but you also have a transparent tile here, too; its at the beginning of the section. keep that blank (i.e. the same color as your transparent color) as that is your blank second layer tile.
thats it, i hope i explained that well; if you have any other questions just write it in this topic.
good luck with your tileset!