TExcelColor uses VCL colors when you use VCL.FlexCel.Core, and FMX colors when you use FMX.FlexCel.Core.
In fact, one of the reasons to have a TExcelColor struct is to isolate from the different TColors in the different platforms.
Now, while TAlphaColor will convert to TExcelColor automatically, the inverse isn't true. You need to specifiaclly convert TExcelColor to TAlphaColor: This is because a TExcelColor can have an indexed color inside, and the RGB color corresponding to the index depends on the color palette. So in order to convert, FlexCel needs to know the color palette of the file, and you need to pass a TExcelFile object to the conversion as TExcelFile has the color palette.